Resist pattern-forming method

ABSTRACT

A resist pattern-forming method includes applying a resist underlayer film-forming composition to a substrate to form a resist underlayer film. The resist underlayer film-forming composition includes (A) a polysiloxane. A radiation-sensitive resin composition is applied to the resist underlayer film to form a resist film. The radiation-sensitive resin composition includes (a1) a polymer that changes in polarity and decreases in solubility in an organic solvent due to an acid. The resist film is exposed. The exposed resist film is developed using a developer that includes an organic solvent.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation application of U.S. patentapplication Ser. No. 14/627,670 filed Feb. 20, 2015, which in turn is acontinuation application of U.S. patent application Ser. No. 14/158,160filed Jan. 17, 2014, which in turn is a continuation application of U.S.patent application Ser. No. 13/434,851 filed Mar. 30, 2012, which inturn is a continuation application of International Application No.PCT/JP2011/069957, filed Sep. 1, 2011, which claims priority to JapanesePatent Application No. 2010-202361, filed Sep. 9, 2010 and to JapanesePatent Application No. 2011-181004, filed Aug. 22, 2011. The contents ofthese applications are incorporated herein by reference in theirentirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a resist pattern-forming method.

2. Discussion of the Background

A reduction in the line width of a resist pattern used for lithographyhas been desired along with miniaturization of the structure ofelectronic devices (e.g., semiconductor devices and liquid crystaldevices). A fine resist pattern having a line width of about 90 nm canbe formed using short-wavelength radiation (e.g., ArF excimer laserlight) and a radiation-sensitive resin composition that responds to suchshort-wavelength radiation. However, it will be required to form a finerresist pattern in the future.

As technology that makes it possible to form a finer pattern byutilizing the characteristics of the radiation-sensitive resincomposition, technology that utilizes an organic solvent having apolarity lower than that of an alkaline aqueous solution as thedeveloper has been proposed (see Japanese Patent Application Publication(KOKAI) No. 2000-199953). This technology makes it possible to increasethe optical contrast, so that a finer pattern can be formed.

However, it will be required to form a resist pattern in a finer area inthe future. A resist pattern-forming method that can deal with variousresist patterns such as a trench pattern (e.g., line-and-space pattern)and a hole pattern (e.g., contact hole pattern), and can form a resistpattern that exhibits an excellent depth of focus and an excellentpattern shape, and also exhibits excellent critical dimension uniformity(CDU) (when forming a hole pattern) or excellent pattern collapseresistance (when forming a trench pattern), has been desired.

SUMMARY OF THE INVENTION

According to one aspect of the present invention, a resistpattern-forming method includes applying a resist underlayerfilm-forming composition to a substrate to form a resist underlayerfilm. The resist underlayer film-forming composition includes (A) apolysiloxane. A radiation-sensitive resin composition is applied to theresist underlayer film to form a resist film. The radiation-sensitiveresin composition includes (a1) a polymer that changes in polarity anddecreases in solubility in an organic solvent due to an acid. The resistfilm is exposed. The exposed resist film is developed using a developerthat includes an organic solvent.

DESCRIPTION OF THE EMBODIMENTS

According to an embodiment of the invention, a resist pattern-formingmethod includes:

(1) applying a resist underlayer film-forming composition to a substrateto form a resist underlayer film, the resist underlayer film-formingcomposition including (A) a polysiloxane;(2) applying a radiation-sensitive resin composition to the resistunderlayer film to form a resist film, the radiation-sensitive resincomposition including (a1) a polymer that changes in polarity anddecreases in solubility in an organic solvent due to an acid(hereinafter may be referred to as “polymer (a1));(3) exposing the resist film; and(4) developing the exposed resist film using a developer that includesan organic solvent.

The resist pattern-forming method can deal with various resist patterns,and can form a resist pattern that exhibits an excellent depth of focus,an excellent pattern shape, high resolution, excellent CDU, andexcellent pattern collapse resistance, by forming the resist underlayerfilm that includes the polysiloxane (A), and developing the resist filmusing the developer that includes an organic solvent. The reasons thatthe above effects are achieved by the above configuration have notnecessarily been clarified. It is conjectured that the polysiloxane (A)included in the resist underlayer film strongly interacts with theresist pattern formed on the resist underlayer film, so that excellentpattern collapse resistance is achieved. It is also conjectured that awide depth of focus is achieved, and the pattern shape, the CDU, and theresolution are improved due to an improvement in pattern collapseresistance.

The resist underlayer film-forming composition may further include (B) anitrogen-containing compound.

It is conjectured that the nitrogen-containing compound (B) present inthe resist underlayer film formed under the resist pattern promotes acrosslinking reaction within the underlayer film, so that the oxygenashing resistance is improved.

The resist underlayer film-forming composition may further include (C) aphotoacid generator (hereinafter may be referred to as “acid generator(C)”).

It is conjectured that dissociation of the acid-labile group included inthe polymer within the resist pattern formed on the resist underlayerfilm is promoted when the resist underlayer film includes the acidgenerator (C), so that the resolution, the pattern collapse resistance,and the like are further improved.

The polymer (a1) preferably includes a structural unit (I) shown by thefollowing formula (1).

wherein R represents a hydrogen atom or a methyl group, and R^(p1),R^(p2), and R^(p3) individually represent a monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, and R^(p2) and R^(p3) may bond to eachother to form a divalent alicyclic hydrocarbon group having 4 to 20carbon atoms together with the carbon atom bonded to R^(p2) and R^(p3).

When the polymer (a1) included in the radiation-sensitive resincomposition includes the above specific structural unit, the resistpattern formed using the radiation-sensitive resin composition includesa carboxyl group, so that interaction with the polysiloxane (A) includedin the resist underlayer film is considered to increase. This furtherimproves the properties of the resist pattern.

The radiation-sensitive resin composition preferably further includes(a2) a polymer that includes at least one structural unit (III) selectedfrom the group consisting of a structural unit shown by a formula (3-1)and a structural unit shown by a formula (3-2) (hereinafter may bereferred to as “polymer (a2)”.

wherein R¹ represents a hydrogen atom, a methyl group, or atrifluoromethyl group, and R² represents a linear or branched alkylgroup having 1 to 6 carbon atoms that includes a fluorine atom, or amonovalent alicyclic group having 4 to 20 carbon atoms that includes afluorine atom, wherein a part or all of the hydrogen atoms of the alkylgroup or the alicyclic hydrocarbon group may be substituted with asubstituent.

wherein R³ represents a hydrogen atom, a methyl group, or atrifluoromethyl group, R⁴ represents an (m+1)-valent linking group, m isan integer from 1 to 3, X represents a divalent linking group thatincludes a fluorine atom, and R⁵ represents a hydrogen atom or amonovalent organic group, and wherein a plurality of X and a pluralityof R⁵ may respectively be either identical or different when m is 2 or3.

When the radiation-sensitive resin composition includes the polymer (a2)that includes the above specific structural unit that includes afluorine atom, the polymer (a2) is unevenly distributed in the surfacelayer of the resulting resist film, so that elution of the acidgenerator and the like from the resist film into the immersion liquidcan be suppressed during liquid immersion lithography. Moreover, it ispossible to implement a higher speed scan due to an increase in thehydrophobicity of the surface of the resist film.

It is preferable that the polymer (a2) does not include an acid-labilegroup. When the polymer (a2) does not include an acid-labile group, theeffect of suppressing elution of the acid generator and the like duringliquid immersion lithography can be improved while improving thehydrophobicity of the surface of the resist film. Moreover, occurrenceof development defects due to insufficient dissolution can be suppressedeven if the polymer (a2) does not include an acid-labile group whenimplementing the resist pattern-forming method that utilizes the organicsolvent as the developer.

The polysiloxane (A) is preferably a hydrolysis-condensation product ofa silane compound shown by the following formula (i).

R^(A) _(a)SiX_(4-a)  (i)

wherein R^(A) represents a hydrogen atom, a fluorine atom, an alkylgroup having 1 to 5 carbon atoms, an alkenyl group, an aryl group, or acyano group, a part or all of the hydrogen atoms of the alkyl group maybe substituted with a glycidyloxy group, an oxetanyl group, an acidanhydride group, or a cyano group, and a part or all of the hydrogenatoms of the aryl group may be substituted with a hydroxyl group, Xrepresents a halogen atom or —OR^(B), R^(B) represents a monovalentorganic group, a is an integer from 0 to 3, and a plurality of R^(A) anda plurality of X may respectively be either identical or different whena plurality of R^(A) and a plurality of X are present.

When the polysiloxane (A) is a hydrolysis-condensation product of theabove specific silane compound, interaction between the resistunderlayer film and the resist pattern formed on the resist underlayerfilm can be improved, so that the resolution, the pattern collapseresistance, and the like of the resist pattern can be further improved.

It is preferable that the resist pattern-forming method be used to format least one pattern selected from the group consisting of a trenchpattern and a hole pattern. Since a pattern that exhibits excellentresolution and CDU can be formed by the resist pattern-forming method,the resist pattern-forming method is particularly suitable for forming ahole pattern (e.g., contact hole pattern). Since a pattern that exhibitsexcellent pattern collapse resistance can be formed by the resistpattern-forming method, the resist pattern-forming method isparticularly suitable for forming a trench pattern (e.g., line-and-spacepattern).

The resist pattern-forming method thus can deal with various resistpatterns, and can form a resist pattern that exhibits an excellent depthof focus, an excellent pattern shape, high resolution, excellent CDU,and excellent pattern collapse resistance.

Resist Pattern-Forming Method

A resist pattern-forming method according to one embodiment of theinvention includes (1) applying a resist underlayer film-formingcomposition to a substrate to form a resist underlayer film, the resistunderlayer film-forming composition including (A) a polysiloxane(hereinafter may be referred to as “step (1)”), (2) applying aradiation-sensitive resin composition to the resist underlayer film toform a resist film, the radiation-sensitive resin composition including(a1) a polymer that changes in polarity and decreases in solubility inan organic solvent due to an acid (hereinafter may be referred to as“step (2)”), (3) exposing the resist film (hereinafter may be referredto as “step (3)”), and (4) developing the exposed resist film using adeveloper that includes an organic solvent (hereinafter may be referredto as “step (4)”). Each step is described in detail below.

Step (1)

In the step (1), the resist underlayer film-forming composition thatincludes the polysiloxane (A) is applied to a substrate to form a resistunderlayer film. The resist underlayer film-forming composition isdescribed later. A silicon wafer, an aluminum-coated wafer, or the likemay be used as the substrate. An organic antireflective film asdisclosed in Japanese Patent Publication (KOKOKU) No. 6-12452, JapanesePatent Application Publication (KOKAI) No. 59-93448, or the like may beformed on the substrate.

The resist underlayer film-forming composition may be applied by spincoating, cast coating, roll coating, or the like. The thickness of theresist film is normally 0.01 to 1 μm, and preferably 0.01 to 0.5 μm.

The resist underlayer film formed by applying the resist underlayerfilm-forming composition may optionally be prebaked (PB) to vaporize thesolvent. The PB temperature is appropriately selected depending on thecomposition of the resist underlayer film-forming composition, but isnormally about 50 to about 450° C. The PB time is normally about 5 toabout 600 seconds.

Step (2)

In the step (2), the radiation-sensitive resin composition is applied tothe resist underlayer film formed by the step (1) to form a resist film,the radiation-sensitive resin composition including the polymer (a1)that changes in polarity and decreases in solubility in an organicsolvent due to an acid. The radiation-sensitive resin composition isdescribed later. The radiation-sensitive resin composition may beapplied in the same manner (i.e., coating method and thickness) as theresist underlayer film-forming composition used in the step (1). The PBtemperature is appropriately selected depending on the composition ofthe radiation-sensitive resin composition, but is normally about 30 toabout 200° C., and preferably 50 to 150° C. The PB time is normallyabout 5 to about 600 seconds.

A protective film as disclosed in Japanese Patent ApplicationPublication (KOKAI) No. 5-188598 or the like may be formed on the resistfilm so that the resist film is not affected by basic impurities and thelike contained in the environmental atmosphere. In order to preventoutflow of the acid generator and the like from the resist film, aliquid immersion lithography protective film as disclosed in JapanesePatent Application Publication (KOKAI) No. 2005-352384 or the like maybe formed on the resist film. These techniques may be used incombination.

Step (3)

In the step (3), the desired area of the resist film formed by the step(2) is exposed through a mask having a specific pattern and an optionalimmersion liquid. The resist film may be successively exposed aplurality of times. For example, the desired area of the resist film maybe subjected to a first exposure through a mask, and then subjected to asecond exposure so that the exposed areas intersect. For example, whenthe exposed areas intersect perpendicularly, it is easy to form acircular contact hole pattern in the unexposed area enclosed by theexposed areas. Examples of the immersion liquid that is optionally usedfor exposure include water, a fluorine-containing inert liquid, and thelike. It is preferable that the immersion liquid be transparent to theexposure wavelength, and have a refractive index temperature coefficientas small as possible so that distortion of an optical image projectedonto the resist film is minimized. When using an ArF excimer laser(wavelength: 193 nm) as the exposure light source, it is preferable touse water from the viewpoint of availability and ease of handling. Whenusing water as the immersion liquid, a small amount of an additive thatdecreases the surface tension of water and increases the surfaceactivity of water may be added to the water. It is preferable that theadditive does not dissolve the resist layer formed on the wafer, anddoes not affect the bottom optical coating of the lens. Distilled wateris preferably used as the water.

Examples of radiation used for exposure include electromagnetic wavessuch as ultraviolet rays, deep ultraviolet rays, X-rays, and γ-rays,charged particle rays such as electron beams and α-rays, and the like.Among these, deep ultraviolet rays are preferable. It is more preferableto use ArF excimer laser light or KrF excimer laser light (wavelength:248 nm). It is still more preferable to use ArF excimer laser light. Theexposure conditions (e.g., dose) are appropriately selected depending onthe composition of the radiation-sensitive resin composition, the typeof additive, and the like. When the resist pattern-forming methodincludes a plurality of exposure steps, an identical or different lightsource may be used in each exposure step. Note that it is preferable touse ArF excimer laser light in the first exposure step.

It is preferable to perform post-exposure bake (PEB) after exposure. Theacid-labile group included in the polymer included in theradiation-sensitive resin composition dissociates smoothly due to PEB,for example. The PEB temperature is normally 30 to 200° C., andpreferably 50 to 170° C. The PEB time is normally 5 to 600 seconds.

Step (4)

In the step (4), the resist film exposed in the step (3) is developedusing the developer that includes the organic solvent to form a pattern.Specifically, the unexposed area and the low-exposed area areselectively dissolved and removed using the developer that includes theorganic solvent. It is preferable that the developer include the organicsolvent as the main component. The content of the organic solvent in thedeveloper is preferably 60 mass % or more, more preferably 70 mass % ormore, still more preferably 80 mass % or more, and particularlypreferably 90 mass % or more. The organic solvent included in thedeveloper is preferably at least one solvent selected from the groupconsisting of alcohol solvents, ether solvents, ketone solvents, amidesolvents, ester solvents, and hydrocarbon solvents.

Examples of the alcohol solvents include monohydric alcohol solventssuch as methanol, ethanol, n-propanol, isopropanol, n-butanol,isobutanol, sec-butanol, t-butanol, n-pentanol, isopentanol,2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol,2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol,n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol,2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonylalcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfurylalcohol, phenol, cyclohexanol, methylcyclohexanol,3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol;

polyhydric alcohol solvents such as ethylene glycol, 1,2-propyleneglycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol,2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethyleneglycol, dipropylene glycol, triethylene glycol, and tripropylene glycol;polyhydric alcohol partial ether solvents such as ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, ethylene glycolmonopropyl ether, ethylene glycol monobutyl ether, ethylene glycolmonohexyl ether, ethylene glycol monophenyl ether, ethylene glycolmono-2-ethyl butyl ether, diethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, diethylene glycol monopropyl ether, diethyleneglycol monobutyl ether, diethylene glycol monohexyl ether, propyleneglycol monomethyl ether, propylene glycol monoethyl ether, propyleneglycol monopropyl ether, propylene glycol monobutyl ether,dipropyleneglycol monomethylether, dipropylene glycol monoethyl ether,and dipropylene glycol monopropyl ether; and the like.

Examples of the ether solvents include dialiphatic ether solvents suchas diethyl ether, ethyl propyl ether, dipropyl ether, dibutyl ether, anddiisopropyl ether;

aromatic ring-containing ether solvents such as anisole, phenyl ethylether, phenyl propyl ether, tolyl methyl ether, tolyl ethyl ether,diphenyl ether, and ditolyl ether;cyclic ether solvents such as tetrahydrofuran, tetrahydropyran, andmethyltetrahydrofuran; and the like.

Examples of the ketone solvents include chain-like ketone solvents suchas acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butylketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone,ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, andtrimethylenonane;

cyclic ketone solvents such as cyclopentanone, cyclohexanone,cycloheptanone, cyclooctanone, and methylcyclohexanone;diketone solvents such as 2,4-pentanedione and acetonylacetone;hydroxyl group-containing ketone solvents such as diacetone alcohol;aromatic ketone solvents such as acetophenone and phenyl ethyl ketone;and the like.

Examples of the amide solvents include N,N′-dimethylimidazolidinone,N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide,acetamide, N-methylacetamide, N,N-dimethylacetamide,N-methylpropionamide, N-methylpyrrolidone, and the like.

Examples of the ester solvents include carboxylate solvents such asmethyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate,n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate,sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate,2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexylacetate, methylcyclohexyl acetate, n-nonyl acetate, glycol diacetate,methoxy triglycol acetate, methyl acetoacetate, ethyl acetoacetate,ethyl propionate, n-butyl propionate, i-amyl propionate, diethyloxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyllactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, anddiethyl phthalate;

polyhydric alcohol monoalkyl ether acetate solvents such as ethyleneglycol monomethyl ether acetate, ethylene glycol monoethyl etheracetate, diethylene glycol monomethyl ether acetate, diethylene glycolmonoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate,propylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate, propylene glycol monopropyl ether acetate, propyleneglycol monobutyl ether acetate, dipropylene glycol monomethyl etheracetate, and dipropylene glycol monoethyl ether acetate;carbonate solvents such as diethyl carbonate and propylene carbonate;lactone solvents such as γ-butyrolactone and γ-valerolactone; and thelike.

Examples of the hydrocarbon solvents include aliphatic hydrocarbonsolvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane,isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane,and methylcyclohexane;

aromatic hydrocarbon solvents such as benzene, toluene, xylene,mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene,n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene,triethylbenzene, diisopropylbenzene, and n-amylnaphthalene;halogen-containing solvents such as dichloromethane, chloroform,fluorocarbon, chlorobenzene, and dichlorobenzene; and the like.

Among these, alcohol solvents, ether solvents, ketone solvents, andester solvents are preferable, ether solvents, ketone solvents, andester solvents are more preferable, and aromatic ring-containing ethersolvents, chain-like ketone solvents, and carboxylate solvents are stillmore preferable. It is particularly preferable to use n-butyl acetate,isopropyl acetate, n-butyl acetate, amyl acetate, methyl n-pentylketone, or anisole. These organic solvents may be used eitherindividually or in combination.

An appropriate amount of surfactant may optionally be added to thedeveloper. An ionic or nonionic fluorine-containing surfactant and/or asilicone surfactant or the like may be used as the surfactant.

Examples of the development method include a dipping method thatimmerses the substrate in a container filled with the developer for agiven time, a puddle method that allows the developer to be present onthe surface of the substrate due to surface tension for a given time, aspray method that sprays the developer onto the surface of thesubstrate, a dynamic dispensing method that applies the developer to thesubstrate that is rotated at a constant speed while scanning with adeveloper application nozzle at a constant speed, and the like.

The resist film developed in the step (4) may be rinsed with a rinseagent. An alkane solvent, a ketone solvent, an ester solvent, an alcoholsolvent, an amide solvent, and the like are preferable as the rinseagent. Among these, an alcohol solvent and an ester solvent arepreferable, and a monohydric alcohol solvent having 6 to 8 carbon atomsis particularly preferable. Examples of the monohydric alcohol solventhaving 6 to 8 carbon atoms include linear, branched, or cyclicmonohydric alcohols such as 1-hexanol, 1-heptanol, 1-octanol,4-methyl-2-pentanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol,3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Among these,1-hexanol, 2-hexanol, 2-heptanol, and 4-methyl-2-pentanol arepreferable, and 4-methyl-2-pentanol is more preferable.

The rinse agent may include one or more types of each component. Thewater content in the rinse agent is preferably 10 mass % or less, morepreferably 5 mass % or less, and particularly preferably 3 mass % orless. If the water content in the rinse agent is 10 mass % or less,excellent developability can be obtained. Note that a surfactant(described later) may be added to the rinse agent.

Examples of the rinse method include a spin method that applies therinse agent to the substrate that is rotated at a constant speed, adipping method that immerses the substrate in a container filled withthe rinse agent for a given time, a spray method that sprays the rinseagent onto the surface of the substrate, and the like.

Resist Underlayer Film-Forming Composition

The resist underlayer film-forming composition includes the polysiloxane(A). The resist underlayer film-forming composition preferably furtherincludes (B) a nitrogen-containing compound, (C) an acid generator, and(D) a solvent. The resist underlayer film-forming composition mayfurther include an additional optional component as long as the effectsof the invention are not impaired. Each component is described below.

Polysiloxane (A)

The polysiloxane (A) is not particularly limited as long as thepolysiloxane (A) is a polymer that includes a siloxane bond, but ispreferably a hydrolysis-condensation product of the silane compoundshown by the formula (i). The polysiloxane (A) may be synthesized usingonly one type of silane compound, or may be synthesized using two ormore types of silane compound.

In the formula (i), R^(A) represents a hydrogen atom, a fluorine atom,an alkyl group having 1 to 5 carbon atoms, an alkenyl group, an arylgroup, or a cyano group, a part or all of the hydrogen atoms of thealkyl group may be substituted with a glycidyloxy group, an oxetanylgroup, an acid anhydride group, or a cyano group, and a part or all ofthe hydrogen atoms of the aryl group may be substituted with a hydroxylgroup, X represents a halogen atom or —OR^(B), R^(B) represents amonovalent organic group, a is an integer from 0 to 3, and a pluralityof R^(A) and a plurality of X may respectively be either identical ordifferent when a plurality of R^(A) and a plurality of X are present.

Examples of the alkyl group having 1 to 5 carbon atoms represented byR^(A) include linear alkyl groups such as a methyl group, an ethylgroup, an n-propyl group, an n-butyl group, and an n-pentyl group;

branched alkyl groups such as an isopropyl group, an isobutyl group, asec-butyl group, a t-butyl group, and an isoamyl group; and the like.

Examples of the alkenyl group represented by R^(A) include a groupobtained by removing one hydrogen atom from an alkene compound, and thelike. Specific examples of the alkenyl group include an ethenyl group, a1-propen-1-yl group, a 1-propen-2-yl group, a 1-propen-3-yl group, a1-buten-1-yl group, a 1-buten-2-yl group, a 1-buten-3-yl group, a1-buten-4-yl group, a 2-buten-1-yl group, a 2-buten-2-yl group, a1-penten-5-yl group, a 2-penten-1-yl group, a 2-penten-2-yl group, a1-hexen-6-yl group, a 2-hexen-1-yl group, a 2-hexen-2-yl group, and thelike. Among these, a group shown by the following formula (i-1) ispreferable.

wherein n is an integer from 0 to 4, and “*” indicates a bonding site.

n is preferably 0 or 1, and more preferably 0 (i.e., vinyl group).

Examples of the aryl group represented by R^(A) include a phenyl group,a naphthyl group, a methylphenyl group, an ethylphenyl group, achlorophenyl group, a bromophenyl group, a fluorophenyl group, and thelike.

Examples of the acid anhydride group that may substitute the alkyl groupinclude a succinic anhydride group, a maleic anhydride group, a glutaricanhydride group, and the like.

Examples of the alkyl group substituted with a glycidyloxy group includea 2-glycidyloxyethyl group, a 3-glycidyloxypropyl group, a4-glycidyloxybutyl group, and the like. Among these, a3-glycidyloxypropyl group is preferable.

Examples of the alkyl group substituted with an oxetanyl group include a3-ethyl-3-oxetanylpropyl group, a 3-methyl-3-oxetanylpropyl group, a3-ethyl-2-oxetanylpropyl group, a 2-oxetanylethyl group, and the like.Among these, a 3-ethyl-3-oxetanylpropyl group is preferable.

Examples of the alkyl group substituted with an acid anhydride groupinclude a 2-succinic anhydride group-substituted ethyl group, a3-succinic anhydride group-substituted propyl group, a 4-succinicanhydride group-substituted butyl group, and the like. Among these, a3-succinic anhydride group-substituted propyl group is preferable.

Examples of the alkyl group substituted with a cyano group include a2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group, and thelike.

Examples of the aryl group substituted with a hydroxyl group include a4-hydroxyphenyl group, a 4-hydroxy-2-methylphenyl group, a4-hydroxynaphthyl group, and the like. Among these, a 4-hydroxyphenylgroup is preferable.

Examples of the halogen atom represented by X include a fluorine atom, achlorine atom, a bromine atom, an iodine atom, and the like.

Examples of the monovalent organic group represented by R^(B) include analkyl group, an alkylcarbonyl group, and the like. A methyl group, anethyl group, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a sec-butyl group, and a t-butyl group are preferable asthe alkyl group. A methylcarbonyl group and an ethylcarbonyl group arepreferable as the alkylcarbonyl group.

a is preferably an integer from 0 to 2, and more preferably 1 or 2.

Specific examples of the silane compound shown by the formula (i)include aromatic ring-containing trialkoxysilanes such asphenyltrimethoxysilane, benzyltrimethoxysilane,phenethyltrimethoxysilane, 4-methylphenyltrimethoxysilane,4-ethylphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane,4-phenoxyphenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane,4-aminophenyltrimethoxysilane, 4-dimethylaminophenyltrimethoxysilane,4-acetylaminophenyltrimethoxysilane, 3-methylphenyltrimethoxysilane,3-ethylphenyltrimethoxysilane, 3-methoxyphenyltrimethoxysilane,3-phenoxyphenyltrimethoxysilane, 3-hydroxyphenyltrimethoxysilane,3-aminophenyltrimethoxysilane, 3-dimethylaminophenyltrimethoxysilane,3-acetylaminophenyltrimethoxysilane, 2-methylphenyltrimethoxysilane,2-ethylphenyltrimethoxysilane, 2-methoxyphenyltrimethoxysilane,2-phenoxyphenyltrimethoxysilane, 2-hydroxyphenyltrimethoxysilane,2-aminophenyltrimethoxysilane, 2-dimethylaminophenyltrimethoxysilane,2-acetylaminophenyltrimethoxysilane,2,4,6-trimethylphenyltrimethoxysilane, 4-methylbenzyltrimethoxysilane,4-ethylbenzyltrimethoxysilane, 4-methoxybenzyltrimethoxysilane,4-phenoxybenzyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane,4-aminobenzyltrimethoxysilane, 4-dimethylaminobenzyltrimethoxysilane,and 4-acetylaminobenzyltrimethoxysilane;

alkyltrialkoxysilanes such as methyltrimethoxysilane,methyltriethoxysilane, methyltri-n-propoxysilane,methyltriisopropoxysilane, methyltri-n-butoxysilane,methyltri-sec-butoxysilane, methyltri-t-butoxysilane,methyltriphenoxysilane, methyltriacetoxysilane, methyltrichlorosilane,methyltriisopropenoxysilane, methyltris(dimethylsiloxy)silane,methyltris(methoxyethoxy)silane, methyltris(methylethylketoxime)silane,methyltris(trimethylsiloxy)silane, methylsilane, ethyltrimethoxysilane,ethyltriethoxysilane, ethyltri-n-propoxysilane,ethyltriisopropoxysilane, ethyltri-n-butoxysilane,ethyltri-sec-butoxysilane, ethyltri-t-butoxysilane,ethyltriphenoxysilane, ethylbistris(trimethylsiloxy)silane,ethyldichlorosilane, ethyltriacetoxysilane, ethyltrichlorosilane,n-propyltrimethoxysilane, n-propyltriethoxysilane,n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane,n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane,n-propyltri-t-butoxysilane, n-propyltriphenoxysilane,n-propyltriacetoxysilane, n-propyltrichlorosilane,isopropyltrimethoxysilane, isopropyltriethoxysilane,isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane,isopropyltri-n-butoxysilane, isopropyltri-sec-butoxysilane,isopropyltri-t-butoxysilane, isopropyltriphenoxysilane,n-butyltrimethoxysilane, n-butyltriethoxysilane,n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane,n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane,n-butyltri-t-butoxysilane, n-butyltriphenoxysilane,n-butyltrichlorosilane, 2-methylpropyltrimethoxysilane,2-methylpropyltriethoxysilane, 2-methylpropyltri-n-propoxysilane,2-methylpropyltriisopropoxysilane, 2-methylpropyltri-n-butoxysilane,2-methylpropyl-tri-sec-butoxysilane, 2-methylpropyltri-t-butoxysilane,2-methylpropyltriphenoxysilane, 1-methylpropyltrimethoxysilane,1-methylpropyltriethoxysilane, 1-methylpropyltri-n-propoxysilane,1-methylpropyltriisopropoxysilane, 1-methylpropyltri-n-butoxysilane,1-methylpropyltri-sec-butoxysilane, 1-methylpropyltri-t-butoxysilane,1-methylpropyltriphenoxysilane, t-butyltrimethoxysilane,t-butyltriethoxysilane, t-butyltri-n-propoxysilane,t-butyltriisopropoxysilane, t-butyltri-n-butoxysilane,t-butyltri-sec-butoxysilane, t-butyltri-t-butoxysilane,t-butyltriphenoxysilane, t-butyltrichlorosilane, andt-butyldichlorosilane;alkenyltrialkoxysilanes such as vinyltrimethoxysilane,vinyltriethoxysilane, vinyltri-n-propoxysilane,vinyltriisopropoxysilane, vinyltri-n-butoxysilane,vinyltri-sec-butoxysilane, vinyltri-t-butoxysilane,vinyltriphenoxysilane, allyltrimethoxysilane, allyltriethoxysilane,allyltri-n-propoxysilane, allyltriisopropoxysilane,allyltri-n-butoxysilane, allyltri-sec-butoxysilane,allyltri-t-butoxysilane, and allyltriphenoxysilane;tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane,tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane,tetra-sec-butoxysilane, and tetra-t-butoxysilane; tetraarylsilanes suchas tetraphenoxysilane;epoxy group-containing silanes such as oxetanyltrimethoxysilane,oxiranyltrimethoxysilane, oxiranylmethyltrimethoxysilane, and3-glycidyloxypropyltrimethoxysilane;acid anhydride group-containing silanes such as3-(trimethoxysilyl)propylsuccinic anhydride,2-(trimethoxysilyl)ethylsuccinic anhydride,3-(trimethoxysilyepropylmaleic anhydride, and2-(trimethoxysilyl)ethylglutaric anhydride;tetrahalosilanes such as tetrachlorosilane; and the like.

Among these, tetramethoxysilane and tetraethoxysilane are preferablesince the resulting resist underlayer film exhibits excellent dryetching resistance.

It is preferable to use phenyltrimethoxysilane,4-methylphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane,4-methylbenzyltrimethoxysilane methyltrimethoxysilane,methyltrimethoxysilane, methyltriethoxysilane,methyltri-n-propoxysilane, methyltriisopropoxysilane,methyltri-n-butoxysilane, methyltri-sec-butoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane,ethyltriisopropoxysilane, ethyltri-n-butoxysilane,ethyltri-sec-butoxysilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, n-propyltri-n-propoxysilane,n-propyltriisopropoxysilane, n-propyltri-n-butoxysilane,n-propyltri-sec-butoxysilane, vinyltrimethoxysilane,vinyltriethoxysilane, allyltrimethoxysilane, or allyltriethoxysilanefrom the viewpoint of reactivity and ease of handling.

It is preferable to use oxetanyltrimethoxysilane,3-glycidyloxypropyltrimethoxysilane, 3-(trimethoxysilyl)propylsuccinicanhydride, or 4-hydroxyphenyltrimethoxysilane from the viewpoint ofimproving the pattern collapse resistance of the resulting resistpattern.

The polysiloxane (A) may be synthesized using an additional silanecompound in addition to the silane compound shown by the formula (i).Examples of the additional silane compound include disilanes such ashexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane,1,1,1,2,2-pentamethoxy-2-methyldisilane,1,1,1,2,2-pentaethoxy-2-methyldisilane,1,1,1,2,2-pentaphenoxy-2-methyldisilane,1,1,1,2,2-pentamethoxy-2-ethyldisilane,1,1,1,2,2-pentaethoxy-2-ethyldisilane,1,1,1,2,2-pentaphenoxy-2-ethyldisilane,1,1,1,2,2-pentamethoxy-2-phenyldisilane,1,1,1,2,2-pentaethoxy-2-phenyldisilane,1,1,1,2,2-pentaphenoxy-2-phenyldisilane,1,1,2,2-tetramethoxy-1,2-dimethyldisilane,1,1,2,2-tetraethoxy-1,2-dimethyldisilane,1,1,2,2-tetraphenoxy-1,2-dimethyldisilane,1,1,2,2-tetramethoxy-1,2-diethyldisilane,1,1,2,2-tetraethoxy-1,2-diethyldisilane,1,1,2,2-tetraphenoxy-1,2-diethyldisilane,1,1,2,2-tetramethoxy-1,2-diphenyldisilane,1,1,2,2-tetraethoxy-1,2-diphenyldisilane,1,1,2,2-tetraphenoxy-1,2-diphenyldisilane,1,1,2-trimethoxy-1,2,2-trimethyldisilane,1,1,2-triethoxy-1,2,2-trimethyldisilane,1,1,2-triphenoxy-1,2,2-trimethyldisilane,1,1,2-trimethoxy-1,2,2-triethyldisilane,1,1,2-triethoxy-1,2,2-triethyldisilane,1,1,2-triphenoxy-1,2,2-triethyldisilane,1,1,2-trimethoxy-1,2,2-triphenyldisilane,1,1,2-triethoxy-1,2,2-triphenyldisilane,1,1,2-triphenoxy-1,2,2-triphenyldisilane,1,2-dimethoxy-1,1,2,2-tetramethyldisilane,1,2-diethoxy-1,1,2,2-tetramethyldisilane,1,2-diphenoxy-1,1,2,2-tetramethyldisilane,1,2-dimethoxy-1,1,2,2-tetraethyldisilane,1,2-diethoxy-1,1,2,2-tetraethyldisilane,1,2-diphenoxy-1,1,2,2-tetraethyldisilane,1,2-dimethoxy-1,1,2,2-tetraphenyldisilane,1,2-diethoxy-1,1,2,2-tetraphenyldisilane,1,2-diphenoxy-1,1,2,2-tetraphenyldisilane, bis(trimethoxysilyl)methane,bis(triethoxysilyl)methane, bis(tri-n-propoxysilyl)methane,bis(triisopropoxysilyl)methane, bis(tri-n-butoxysilyl)methane,bis(tri-sec-butoxysilyl)methane, bis(tri-t-butoxysilyl)methane,1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane,1,2-bis(tri-n-propoxysilyl)ethane, 1,2-bis(triisopropoxysilyl)ethane,1,2-bis(tri-n-butoxysilyl)ethane, 1,2-bis(tri-sec-butoxysilyl)ethane,1,2-bis(tri-t-butoxysilyl)ethane,1-(dimethoxymethylsilyl)-1-(trimethoxysilyl)methane,1-(diethoxymethylsilyl)-1-(triethoxysilyl)methane,1-(di-n-propoxymethylsilyl)-1-(tri-n-propoxysilyl)methane,1-(diisopropoxymethylsilyl)-1-(triisopropoxysilyl)methane,1-(di-n-butoxymethylsilyl)-1-(tri-n-butoxysilyl)methane,1-(di-sec-butoxymethylsilyl)-1-(tri-sec-butoxysilyl)methane,1-(di-t-butoxymethylsilyl)-1-(tri-t-butoxysilyl)methane,1-(dimethoxymethylsilyl)-2-(trimethoxysilyl)ethane,1-(diethoxymethylsilyl)-2-(triethoxysilyflethane,1-(di-n-propoxymethylsilyl)-2-(tri-n-propoxysilyl)ethane,1-(diisopropoxymethylsilyl)-2-(triisopropoxysilyl)ethane,1-(di-n-butoxymethylsilyl)-2-(tri-n-butoxysilyl)ethane,1-(di-sec-butoxymethylsilyl)-2-(tri-sec-butoxysilyl)ethane,1-(di-t-butoxymethylsilyl)-2-(tri-t-butoxysilyl)ethane,bis(dimethoxymethylsilyl)methane, bis(diethoxymethylsilyl)methane,bis(di-n-propoxymethylsilyl)methane,bis(diisopropoxymethylsilyl)methane, bis(di-n-butoxymethylsilyl)methane,bis(di-sec-butoxymethylsilyl)methane,bis(di-t-butoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane,1,2-bis(diethoxymethylsilyl)ethane,1,2-bis(di-n-propoxymethylsilyl)ethane,1,2-bis(diisopropoxymethylsilyl)ethane,1,2-bis(di-n-butoxymethylsilyl)ethane,1,2-bis(di-sec-butoxymethylsilyl)ethane,1,2-bis(di-t-butoxymethylsilyl)ethane, bis(dimethylmethoxysilyl)methane,bis(dimethylethoxysilyl)methane, bis(dimethyl-n-propoxysilyl)methane,bis(dimethylisopropoxysilyl)methane, bis(dimethyl-n-butoxysilyl)methane,bis(dimethyl-sec-butoxysilyl)methane,bis(dimethyl-t-butoxysilyl)methane, 1,2-bis(dimethylmethoxysilyl)ethane,1,2-bis(dimethylethoxysilyl)ethane,1,2-bis(dimethyl-n-propoxysilyl)ethane,1,2-bis(dimethylisopropoxysilyl)ethane,1,2-bis(dimethyl-n-butoxysilyl)ethane,1,2-bis(dimethyl-sec-butoxysilyl)ethane,1,2-bis(dimethyl-t-butoxysilyl)ethane,1-(dimethoxymethylsilyl)-1-(trimethylsilyl)methane,1-(diethoxymethylsilyl)-1-(trimethylsilyl)methane,1-(di-n-propoxymethylsilyl)-1-(trimethylsilyl)methane,1-(diisopropoxymethylsilyl)-1-(trimethylsilyl)methane,1-(di-n-butoxymethylsilyl)-1-(trimethylsilyl)methane,1-(di-sec-butoxymethylsilyl)-1-(trimethylsilyl)methane,1-(di-t-butoxymethylsilyl)-1-(trimethylsilyl)methane,1-(dimethoxymethylsilyl)-2-(trimethylsilyl)ethane,1-(diethoxymethylsilyl)-2-(trimethylsilyl)ethane,1-(di-n-propoxymethylsilyl)-2-(trimethylsilyl)ethane,1-(diisopropoxymethylsilyl)-2-(trimethylsilyl)ethane,1-(di-n-butoxymethylsilyl)-2-(trimethylsilyl)ethane,1-(di-sec-butoxymethylsilyl)-2-(trimethylsilyl)ethane,1-(di-t-butoxymethylsilyl)-2-(trimethylsilyl)ethane,1,2-bis(trimethoxysilyl)benzene, 1,2-bis(triethoxysilyl)benzene,1,2-bis(tri-n-propoxysilyl)benzene, 1,2-bis(triisopropoxysilyl)benzene,1,2-bis(tri-n-butoxysilyl)benzene, 1,2-bis(tri-sec-butoxysilyl)benzene,1,2-bis(tri-t-butoxysilyl)benzene, 1,3-bis(trimethoxysilyl)benzene,1,3-bis(triethoxysilyl)benzene, 1,3-bis(tri-n-propoxysilyl)benzene,1,3-bis(triisopropoxysilyl)benzene, 1,3-bis(tri-n-butoxysilyl)benzene,1,3-bis(tri-sec-butoxysilyl)benzene, 1,3-bis(tri-t-butoxysilyl)benzene,1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene,1,4-bis(tri-n-propoxysilyl)benzene, 1,4-bis(triisopropoxysilyl)benzene,1,4-bis(tri-n-butoxysilyl)benzene, 1,4-bis(tri-sec-butoxysilyl)benzene,and 1,4-bis(tri-t-butoxysilyl)benzene; polycarbosilanes such aspolydimethoxymethylcarbosilane and polydiethoxymethylcarbosilane; andthe like.

The content of the polysiloxane (A) in the resist underlayerfilm-forming composition is preferably 80 mass % or more, morepreferably 90 mass % or more, and still more preferably 95 mass % ormore, based on the total solid content of the resist underlayerfilm-forming composition. The resist underlayer film-forming compositionmay include only one type of the polysiloxane (A), or may include two ormore types of the polysiloxane (A).

The polystyrene-reduced weight average molecular weight (Mw) of thepolysiloxane (A) determined by size exclusion chromatography is normally500 to 50,000, preferably 1000 to 30,000, and more preferably 1000 to15,000.

The term “polystyrene-reduced weight average molecular weight (Mw)” usedherein refers to a value measured by gel permeation chromatography (GPC)using GPC columns manufactured by Tosoh Corporation (G2000HXL×2,G3000HXL×1, G4000HXL×1) (standard: monodisperse polystyrene, flow rate:1.0 ml/min, eluant: tetrahydrofuran, column temperature: 40° C.).

The silane compound shown by the formula (i) and an optional additionalsilane compound may be subjected to hydrolysis and condensation by aknown method.

Nitrogen-Containing Compound (B)

The nitrogen-containing compound (B) is a compound that includes a basicamino group, or a compound that includes a group that produces a basicamino group due to an acid. The nitrogen-containing compound (B)improves the ashing resistance and the like of the resist underlayerfilm formed using the resist underlayer film-forming composition. It isconjectured that the nitrogen-containing compound (B) present in theresist underlayer film promotes a crosslinking reaction within theunderlayer film, so that the ashing resistance and the like of theresist underlayer film are improved. Examples of the nitrogen-containingcompound (B) include compounds used as the acid diffusion controller (C)included in the radiation-sensitive resin composition, and the like.Further examples of the nitrogen-containing compound (B) include anitrogen-containing compound that includes an ester group and at leastone polar group selected from a hydroxyl group and a carboxyl group, anitrogen-containing compound that includes at least one group selectedfrom a hydroxyl group, a carboxyl group, and an ether group, anitrogen-containing compound that includes an ester group, and the like.

Examples of the nitrogen-containing compound that includes an estergroup and at least one polar group selected from a hydroxyl group and acarboxyl group include the compounds shown by the following formulas(B-1-1) to (B-1-5), and the like.

Examples of the nitrogen-containing compound that includes at least onegroup selected from a hydroxyl group, a carboxyl group, and an ethergroup include the compounds shown by the following formulas (B-2-1) to(B-2-4), and the like. Examples of the nitrogen-containing compound thatincludes an ester group include the compounds shown by the followingformulas (B-3-1) to (B-3-4), and the like.

R in the formulas (B-2-2) and (B-2-3) represents an alkyl group having 1to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.

Among these, the nitrogen-containing compound that includes an estergroup and at least one polar group selected from a hydroxyl group and acarboxyl group is preferable, and the compound shown by the formula(B-1-1) and the compound shown by the formula (B-1-2) are morepreferable. When the nitrogen-containing compound includes an estergroup and at least one polar group selected from a hydroxyl group and acarboxyl group, sublimation of the nitrogen-containing compound (B) issuppressed when baking the resist underlayer film, so that thenitrogen-containing compound (B) remains in the resist underlayer film,and sufficiently exhibits the above effect.

These nitrogen-containing compounds (B) may be used either individuallyor in combination. The nitrogen-containing compound (B) is normally usedin an amount of 30 parts by mass or less, preferably 10 parts by mass orless, and more preferably 1 parts by mass or less, based on 100 parts bymass of the polysiloxane (A), from the viewpoint of obtaining anexcellent pattern shape.

Acid Generator (C)

The acid generator (C) is a component that generates an acid uponexposure. When the resist underlayer film includes the acid generator(C), dissociation of the acid-labile group included in the polymerwithin the resist film (pattern) is promoted due to the catalytic effectof an acid generated upon exposure. This improves the resolution and thepattern collapse resistance of the resist pattern. The acid generator(C) may be included in the resist underlayer film-forming composition asa compound (described below), and/or may be included in the polymer.

Examples of the acid generator (C) include onium salts such as sulfoniumsalts, iodonium salts, and tetrahydrothiophenium salts,N-sulfonyloxyimide compounds, organic halogen compounds, sulfonecompounds such as disulfones and diazomethanesulfones, and the like.

Examples of the sulfonium salts include triphenylsulfonium saltcompounds such as triphenylsulfonium trifluoromethanesulfonate,triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfoniumperfluoro-n-octanesulfonate, triphenylsulfonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,triphenylsulfonium2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonate,triphenylsulfonium N,N′-bis(nonafluoro-n-butanesulfonyl)imidate,triphenylsulfonium salicylate, triphenylsulfonium camphorsulfonate, andtriphenylsulfoniumtricyclo[3.3.1.1^(3,7)]decanyldifluoromethanesulfonate;4-cyclohexylphenyldiphenylsulfonium salt compounds such as4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate,4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate,4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate,4-cyclohexylphenyldiphenylsulfonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,4-cyclohexylphenyldiphenylsulfonium2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonate,4-cyclohexylphenyldiphenylsulfoniumN,N′-bis(nonafluoro-n-butanesulfonyl)imidate, and4-cyclohexylphenyldiphenylsulfonium camphorsulfonate;4-t-butylphenyldiphenylsulfonium salt compounds such as4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate,4-t-butylphenyldiphenyl sulfonium nonafluoro-n-butanesulfonate,4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate,4-t-butylphenyldiphenylsulfonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,4-t-butylphenyldiphenylsulfonium2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonate,4-t-butylphenyldiphenylsulfoniumN,N′-bis(nonafluoro-n-butanesulfonyl)imidate, and4-t-butylphenyldiphenylsulfonium camphorsulfonate;tri(4-t-butylphenyl)sulfonium salt compounds such astri(4-t-butylphenyl)sulfonium trifluoromethanesulfonate,tri(4-t-butylphenyl)sulfonium nonafluoro-n-butanesulfonate,tri(4-t-butylphenyl)sulfonium perfluoro-n-octanesulfonate,tri(4-t-butylphenyl)sulfonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,tri(4-t-butylphenyl)sulfonium2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonate,tri(4-t-butylphenyl)sulfoniumN,N′-bis(nonafluoro-n-butanesulfonyl)imidate, andtri(4-t-butylphenyl)sulfonium camphorsulfonate; and the like.

Examples of the iodonium salts include diphenyliodonium salt compoundssuch as diphenyliodonium trifluoromethanesulfonate, diphenyliodoniumnonafluoro-n-butanesulfonate, diphenyliodoniumperfluoro-n-octanesulfonate, diphenyliodonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,diphenyliodonium2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonate,diphenyliodonium N,N′-bis(nonafluoro-n-butanesulfonyl)imidate, anddiphenyliodonium camphorsulfonate; bis(4-t-butylphenyl)iodonium saltcompounds such as bis(4-t-butylphenyl)iodoniumtrifluoromethanesulfonate, bis(4-t-butylphenyl)iodoniumnonafluoro-n-butanesulfonate, bis(4-t-butylphenyl)iodoniumperfluoro-n-octanesulfonate, bis(4-t-butylphenyl)iodonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,bis(4-t-butylphenyl)iodonium2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonate,bis(4-t-butylphenyl)iodoniumN,N′-bis(nonafluoro-n-butanesulfonyl)imidate, andbis(4-t-butylphenyl)iodonium camphorsulfonate; and the like.

Examples of the tetrahydrothiophenium salts include1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium salt compounds suchas 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiopheniumtrifluoromethanesulfonate,1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiopheniumnonafluoro-n-butanesulfonate,1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiopheniumperfluoro-n-octanesulfonate,1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonate,1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiopheniumN,N′-bis(nonafluoro-n-butanesulfonyl)imidate, and1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium camphorsulfonate;1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium salt compoundssuch as 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiopheniumtrifluoromethanesulfonate,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiopheniumnonafluoro-n-butanesulfonate,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiopheniumperfluoro-n-octanesulfonate,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonate,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiopheniumN,N′-bis(nonafluoro-n-butanesulfonyl)imidate, and1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium camphorsulfonate;and the like.

Examples of the N-sulfonyloxyimide compounds include succinimidecompounds such as N-(trifluoromethanesulfonyloxy)succinimide,N-(nonafluoro-n-butanesulfonyloxy)succinimide,N-(perfluoro-n-octanesulfonyloxy)succinimide,N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)succinimide,N-(2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonyloxy)succinimide,and N-(camphorsulfonyloxy)succinimide;bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide compounds such asN-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,and N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide;and the like. Among these, the sulfonium salts are preferable, thetriphenylsulfonium salt compounds are more preferable, andtriphenylsulfonium trifluoromethanesulfonate and triphenylsulfoniumtricyclo[3.3.1.1^(3.7)]decanyldifluoromethanesulfonate are still morepreferable. These acid generators (C) may be used either individually orin combination.

The acid generator (C) is normally used in an amount of 30 parts by massor less, preferably 20 parts by mass or less, more preferably 10 partsby mass or less, and particularly preferably 1 parts by mass or less,based on 100 parts by mass of the polysiloxane (A), from the viewpointof obtaining an excellent pattern shape.

Solvent (D)

The resist underlayer film-forming composition normally includes thesolvent (D). A known organic solvent may be used as the solvent (D), forexample. Examples of the solvent (D) include the organic solvents thatmay be used as the developer in the step (4) of the resistpattern-forming method. The solvent (D) is preferably an alcohol solventor an ester solvent, more preferably a polyhydric alcohol partial ethersolvent or a polyhydric alcohol monoalkyl ether acetate solvent, andstill more preferably propylene glycol monoethyl ether, propylene glycolmonopropyl ether, or propylene glycol monomethyl ether acetate.

The resist underlayer film-forming composition may include water. Thesilicon-containing compound is hydrated due to water, so that thestorage stability of the resist underlayer film-forming composition isimproved. Moreover, a curing reaction is promoted when forming theresist underlayer film, so that a dense film can be obtained. Water ispreferably used in an amount of 0 to 30 parts by mass, more preferably0.1 to 20 parts by mass, and still more preferably 0.2 to 15 parts bymass, based on 100 parts by mass of the solvent (D). If the amount ofwater is too large, the storage stability and the uniformity of the filmmay deteriorate.

Additional Optional Component

The resist underlayer film-forming composition may further include abeta-diketone, colloidal silica, colloidal alumina, an organic polymer,a surfactant, a base generator, or the like as an additional optionalcomponent.

Preparation of Resist Underlayer Film-Forming Composition

The resist underlayer film-forming composition may be prepared by anarbitrary method. For example, the resist underlayer film-formingcomposition may be prepared by dissolving or dispersing the polysiloxane(A), the nitrogen-containing compound (B) (optional), the acid generator(C) (optional), and an additional optional component in the solvent (D).The solid content of the resist underlayer film-forming composition isnormally 0.5 to 20 mass %, and preferably 1 to 15 mass %.

Radiation-Sensitive Resin Composition

The radiation-sensitive resin composition includes the polymer (a1) thatchanges in polarity and decreases in solubility in an organic solventdue to an acid. The radiation-sensitive resin composition may preferablyinclude (a2) a polymer and (b) a photoacid generator (hereinafter may bereferred to as “acid generator (b)”), and may also include an additionaloptional component as long as the effects of the invention are notimpaired. Each component is described in detail below.

Polymer (a1)

The polymer (a1) changes in polarity and decreases in solubility in anorganic solvent due to an acid. The polymer (a1) is preferably a polymerthat includes an acid-labile group, and more preferably a polymer thatincludes the structural unit (I) shown by the formula (1).

Structural Unit (I)

The structural unit (I) is shown by the formula (1).

In the formula (1), R represents a hydrogen atom or a methyl group, andR^(p1), R^(p2), and R^(p3) individually represent a monovalenthydrocarbon group having 1 to 20 carbon atoms, and optionally R^(p2) andR^(p3) may bond to each other to form a divalent alicyclic hydrocarbongroup having 4 to 20 carbon atoms together with the carbon atom bondedto R^(p2) and R^(p3).

The monovalent hydrocarbon group having 1 to 20 carbon atoms representedby R^(p1), R^(p2), and R^(p3) is preferably a chain-like hydrocarbongroup having 1 to 4 carbon atoms or an alicyclic hydrocarbon grouphaving 4 to 20 carbon atoms. The alicyclic hydrocarbon group may be amonoalicyclic hydrocarbon group, or may be a polyalicyclic hydrocarbongroup.

The term “monoalicyclic hydrocarbon group” used herein refers to amonocyclic group that does not include an aromatic group, and the term“polyalicyclic hydrocarbon group” used herein refers to a polycyclicgroup that does not include an aromatic group. Since the polymer (a1)does not include a structural unit that includes an aromatic grouphaving strong absorption at 193 nm, a deterioration in sensitivity andpattern shape can be suppressed.

Examples of the monoalicyclic hydrocarbon group include a group derivedfrom cyclopentane, cyclohexane, or the like. Examples of thepolyalicyclic hydrocarbon group include a group derived from adamantane,norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like.When the acid-labile group includes an alicyclic hydrocarbon group, apart or all of the hydrogen atoms of the alicyclic hydrocarbon group maybe substituted with an alkyl group having 1 to 8 carbon atoms.

Examples of the structural unit (I) include the structural units shownby the following formulas (1-1) to (1-14), and the like. The structuralunits shown by the formulas (1-1) to (1-14) are structural units derivedfrom a methacrylate. Note that the structural unit (I) may be astructural unit that is derived from an acrylate and has a structuresimilar to that of any of the structural units shown by the formulas(1-1) to (1-14).

Among these, the structural units shown by the formulas (1-1), (1-3),(1-9), and (1-14) are preferable.

The content of the structural unit (I) in the polymer (a1) is preferably30 to 70 mol % based on the total structural units included in thepolymer (a1). The polymer (a1) may include only one type of thestructural unit (I), or may include two or more types of the structuralunit (I).

Structural Unit (II)

It is preferable that the polymer (a1) include a structural unit (II)that includes a lactone-containing group or a cycliccarbonate-containing group and is derived from an acrylate. If thepolymer (a1) includes the structural unit (II), the resist film formedusing the radiation-sensitive resin composition exhibits improvedadhesion to the substrate and improved affinity to the developer. Theterm “lactone-containing group” used herein refers to a group thatincludes one ring (lactone ring) that includes a structure shown by—O—C(O)—. The term “cyclic carbonate-containing group” used hereinrefers to a cyclic group that includes one ring (cyclic carbonate ring)that includes a bond shown by —O—C(O)—O—. Examples of the structuralunit (II) include the structural units shown by the following formulas(2-1) to (2-19), and the like.

Among these, the structural units that include a lactone-containinggroup and are derived from an acrylate are preferable, and thestructural unit shown by the formula (2-1) and the structural unit shownby the formula (2-3) are more preferable.

The content of the structural unit (II) in the polymer (a1) ispreferably 20 to 70 mol %, and more preferably 30 to 60 mol %, based onthe total structural units included in the polymer (a1).

Additional Structural Unit

The polymer (a1) may further include an additional structural unit suchas a structural unit that is derived from a (meth)acrylate that includesa polar group (e.g., hydroxyl group, carboxyl group, cyano group, andketonic carbonyl group), or a non-acid-labile structural unit that isderived from a (meth)acrylate and includes an alicyclic structure.Examples of a structural unit derived from a (meth)acrylate thatincludes a hydroxyl group include a structural unit derived from3-hydroxy-1-adamantyl (meth)acrylate, a structural unit derived from2-hydroxyethyl (meth)acrylate, and the like. Examples of a structuralunit derived from a (meth)acrylate that includes a cyano group include astructural unit derived from 2-cyanomethyl-2-adamantyl (meth)acrylate, astructural unit derived from 2-cyanoethyl (meth)acrylate, and the like.Examples of a structural unit derived from a (meth)acrylate thatincludes a ketonic carbonyl group include a structural unit derived from4-oxo-1-adamantyl (meth)acrylate, a structural unit derived from5-oxo-[2.2.1]hept-2-yl (meth)acrylate, and the like.

The content of the additional structural unit in the polymer (a1) isnormally 30 mol % or less, and preferably 20 mol % or less, based on thetotal structural units included in the polymer (a1).

Polymer (a2)

The polymer (a2) includes a structural unit (III). When theradiation-sensitive resin composition includes the polymer (a2) thatincludes the above specific structural unit that includes a fluorineatom, the polymer (a2) is unevenly distributed in the surface layer ofthe resulting resist film, so that elution of the acid generator (b) andthe like from the resist film into the immersion liquid can besuppressed during liquid immersion lithography. Moreover, it is possibleto implement a higher speed scan due to an increase in thehydrophobicity of the surface of the resist film.

The structural unit (III) is at least one structural unit selected fromthe group consisting of a structural unit (III-1) shown by the formula(3-1) and a structural unit (III-2) shown by the formula (3-2).

Structural Unit (III-1)

The structural unit (III-1) is shown by the formula (3-1).

In the formula (3-1), R¹ represents a hydrogen atom, a methyl group, ora trifluoromethyl group, and R² represents a linear or branched alkylgroup having 1 to 6 carbon atoms that includes a fluorine atom, or amonovalent alicyclic group having 4 to 20 carbon atoms that includes afluorine atom, wherein a part or all of the hydrogen atoms of the alkylgroup or the alicyclic hydrocarbon group may be substituted with asubstituent.

Examples of the linear or branched alkyl group having 1 to 6 carbonatoms include a methyl group, an ethyl group, an n-propyl group, ann-butyl group, and the like.

Examples of the monovalent alicyclic hydrocarbon group having 4 to 20carbon atoms include a cyclopentyl group, a cyclopentylpropyl group, acyclohexyl group, a cyclohexylmethyl group, a cycloheptyl group, acyclooctyl group, a cyclooctylmethyl group, and the like.

Examples of a monomer that produces the structural unit (III-1) includetrifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate,perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate,perfluoro-i-propyl (meth)acrylate, perfluoro-n-butyl (meth)acrylate,perfluoro-i-butyl (meth)acrylate, perfluoro-t-butyl (meth)acrylate,perfluorocyclohexyl (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoro)propyl(meth)acrylate, 1-(2,2,3,3,4,4,5,5-octafluoro)pentyl (meth)acrylate,1-(2,2,3,3,4,4,5,5-octafluoro)hexyl (meth)acrylate,perfluorocyclohexylmethyl (meth)acrylate,1-(2,2,3,3,3-pentafluoro)propyl (meth)acrylate,1-(2,2,3,3,4,4,4-heptafluoro)pentyl (meth)acrylate,1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro)decyl(meth)acrylate, 1-(5-trifluoromethyl-3,3,4,4,5,6,6,6-octafluoro)hexyl(meth)acrylate, and the like.

Examples of the structural unit (III-1) include structural units shownby the following formulas (3-1-1) and (3-1-2), and the like.

wherein R¹ is the same as defined for the formula (3-1).

The content of the structural unit (III-1) in the polymer (a2) ispreferably 40 to 100 mol % based on the total structural units includedin the polymer (a2). The polymer (a2) may include only one type of thestructural unit (III-1), or may include two or more types of thestructural unit (III-1).

Structural Unit (III-2)

The structural unit (III-2) is shown by the formula (3-2).

In the formula (3-2), R³ represents a hydrogen atom, a methyl group, ora trifluoromethyl group, R⁴ represents an (m+1)-valent linking group, mis an integer from 1 to 3, X represents a divalent linking group thatincludes a fluorine atom, and R⁵ represents a hydrogen atom or amonovalent organic group, wherein a plurality of X and a plurality of R⁵may respectively be either identical or different when m is 2 or 3.

Examples of the (m+1)-valent linking group represented by R⁴ includethose mentioned above in connection with R¹ in the formula (3-2). WhenR⁴ represents a hydrocarbon group, an oxygen atom, a sulfur atom, —NR′—,a carbonyl group, —COO—, or —CONH— may be bonded to the end of R⁴ thatis bonded to X. Note that R¹ represents a hydrogen atom or a monovalentorganic group.

The divalent linking group represented by X in the formula (3-2) ispreferably a chain-like hydrocarbon group having 1 to 20 carbon atomsthat includes a fluorine atom.

Examples of the divalent linking group represented by X include thegroups (structures) shown by the following formulas (X-1) to (X-6).

X preferably represents the group shown by the formula (X-1).

Examples of the structural unit (III-2) include structural units shownby the following formulas (3-2-1) and (3-2-2), and the like.

In the formula (3-2-1), R⁴ represents a divalent linear, branched, orcyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbonatoms, and R³, X, and R⁵ are the same as defined for the formula (3-2).

In the formula (3-2-2), R³, X, R⁵, and m are the same as defined for theformula (3-2), wherein a plurality of X and a plurality of R⁵ mayrespectively be either identical or different when m is 2 or 3.

Examples of the structural unit shown by the formula (3-2-1) includestructural units shown by the following formulas (3-2-1-1) and(3-2-1-2), and the like. Examples of the structural unit shown by theformula (3-2-2) include a structural unit shown by the following formula(3-2-2-1), and the like.

wherein R³ is the same as defined for the formula (3-2).

Examples of a monomer that produces the repeating unit (III) include(1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) (meth)acrylate,(1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) (meth)acrylate,(1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-5-pentyl) (meth)acrylate,(1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) (meth)acrylate,2-{[5-(1′,1′,1′-trifluoro-2′-trifluoromethyl-2′-hydroxy)propyl]bicyclo[2.2.1]heptyl}(meth)acrylate,and the like.

The content of the structural unit (III) in the polymer (a2) ispreferably 30 to 100 mol % based on the total structural units includedin the polymer (a2). The polymer (a2) may include only one type of thestructural unit (III), or may include two or more types of thestructural unit (III).

The polymer (a2) may further include one or more additional structuralunits such as a structural unit that includes a lactone structure andimproves the solubility in the developer (mentioned above in connectionwith the polymer (a1)), a structural unit that includes an alicycliccompound and improves the etching resistance, and a structural unit thatis derived from an aromatic compound and suppresses reflection from thesubstrate.

It is preferable that the polymer (a2) does not include an acid-labilegroup. When the polymer (a2) does not include an acid-labile group, theeffect of suppressing elution of the acid generator and the like duringliquid immersion lithography can be improved while improving thehydrophobicity of the surface of the resist film. Moreover, occurrenceof development defects due to insufficient dissolution can be suppressedeven if the polymer (a2) does not include an acid-labile group whenimplementing the resist pattern-forming method that utilizes the organicsolvent as the developer.

Synthesis of Polymers (a1) and (a2)

The polymers (a1) and (a2) may be synthesized by polymerizing a monomerthat produces each structural unit in an appropriate solvent using aradical initiator, for example.

The polymerization temperature is normally 40 to 150° C., and preferably50 to 120° C. The polymerization time is normally 1 to 48 hours, andpreferably 1 to 24 hours.

The Mw of the polymer (a1) is preferably 1000 to 50,000, more preferably1000 to 30,000, and particularly preferably 1000 to 10,000. If the Mw ofthe polymer (a1) is within the above range, the polymer (a1) exhibitssufficient solubility in the solvent, and provides the resist patternwith excellent dry etching resistance and an excellent shape.

The ratio (Mw/Mn) of the Mw to the polystyrene-reduced number averagemolecular weight (Mn) of the polymer (a1) determined by GPC is normally1 to 3, and preferably 1 to 2.

The Mw of the polymer (a2) determined by GPC is preferably 1000 to50,000, more preferably 1000 to 30,000, and particularly preferably 1000to 10,000. If the Mw of the polymer (a2) is less than 1000, a sufficientreceding contact angle may not be obtained. If the Mw of the polymer(a2) exceeds 50,000, the resulting resist may exhibit lowdevelopability.

The ratio (Mw/Mn) of the Mw to the Mn of the polymer (a2) is normally 1to 3, and preferably 1 to 2.

Acid Generator (B)

The acid generator (B) included in the radiation-sensitive resincomposition generates an acid upon exposure. The acid-labile group orthe like included in the polymer (A) dissociates due to the acidgenerated by the acid generator (B), and produces a polar group (e.g.,carboxyl group). As a result, the solubility of the polymer (a1) in theorganic solvent decreases. The acid generator (B) may be included in theradiation-sensitive resin composition as a compound (described below)and/or may be included in the polymer.

Examples of the acid generator (B) include onium salt compounds,sulfonimide compounds, halogen-containing compounds, diazoketonecompounds, and the like. Among these, it is preferable to use an oniumsalt compound as the acid generator (B).

Examples of the onium salt compounds include onium salts such assulfonium salts, tetrahydrothiophenium salts, iodonium salts, andphosphonium salts, N-sulfonyloxyimide compounds, diazonium salts,pyridinium salts, and the like.

Examples of the sulfonium salts include triphenylsulfoniumtrifluoromethanesulfonate, triphenylsulfoniumnonafluoro-n-butanesulfonate, triphenylsulfoniumperfluoro-n-octanesulfonate, triphenylsulfonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,triphenylsulfonium camphorsulfonate, triphenylsulfonium2-(1-adamantyl)-1,1-difluoroethanesulfonate,4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate,4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate,4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate,4-cyclohexylphenyldiphenylsulfonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,4-cyclohexylphenyldiphenylsulfonium camphorsulfonate,4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate,4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate,4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate,4-methanesulfonylphenyldiphenylsulfonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,4-methanesulfonylphenyldiphenylsulfonium camphorsulfonate,triphenylphosphonium1,1,2,2-tetrafluoro-6-(1-adamantanecarbonyloxy)-hexane-1-sulfonate, andthe like.

Examples of the tetrahydrothiophenium salts include1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiopheniumtrifluoromethanesulfonate,1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiopheniumnonafluoro-n-butanesulfonate,1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiopheniumperfluoro-n-octanesulfonate,1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium camphorsulfonate,1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiopheniumtrifluoromethanesulfonate,1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiopheniumnonafluoro-n-butanesulfonate,1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiopheniumperfluoro-n-octanesulfonate,1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,1-(6-n-butoxynaphthalen2-yl)tetrahydrothiophenium camphorsulfonate,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiopheniumtrifluoromethanesulfonate,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiopheniumnonafluoro-n-butanesulfonate,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiopheniumperfluoro-n-octanesulfonate,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium camphorsulfonate,and the like.

Examples of the iodonium salts include diphenyliodoniumtrifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate,diphenyliodonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodoniumtrifluoromethanesulfonate, bis(4-t-butylphenyl)iodoniumnonafluoro-n-butanesulfonate, bis(4-t-butylphenyl)iodoniumperfluoro-n-octanesulfonate, bis(4-t-butylphenyl)iodonium2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate,bis(4-t-butylphenyl)iodonium camphorsulfonate, and the like.

Examples of the N-sulfonyloxyimide compounds includeN-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(2-(3-tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecanyl)-1,1-difluoroethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, andthe like.

Among these, onium salts are preferable, and sulfonium salts are morepreferable. It is particularly preferable to use triphenylsulfonium1,1,2,2-tetrafluoro-6-(1-adamantanecarbonyloxy)hexane-1-sulfonate,4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, ortriphenylsulfonium 2-(1-adamantyl)-1,1-difluoroethanesulfonate.

These acid generators (b) may be used either individually or incombination. The acid generator (b) is normally used in an amount of 0.1to 20 parts by mass, and preferably 0.5 to 15 parts by mass, based on100 parts by mass of the polymer (a1), so that the resulting resistexhibits sufficient sensitivity and developability. If the amount of theacid generator (b) is less than 0.1 parts by mass, the sensitivity andthe developability may deteriorate. If the amount of the acid generator(b) exceeds 20 parts by mass, the desired resist pattern may not beobtained due to a decrease in radiation transmittance. The acidgenerator (b) may be included in the polymer (a1) as a structural unitusing a (meth)acrylate that has the above onium salt structure.

Additional Optional Component

The radiation-sensitive resin composition may include (c) an aciddiffusion controller, (d) a solvent, an alicyclic skeleton-containingcompound, a surfactant, a sensitizer, and the like as additionaloptional components in addition to the polymer (a1), the polymer (a2),and the acid generator (b), as long as the effects of the invention arenot impaired.

Acid Diffusion Controller (c)

The acid diffusion controller (c) controls diffusion of an acidgenerated by the acid generator (b) upon exposure within the resistfilm, and suppresses undesired chemical reactions in the unexposed area.This makes it possible to further improve the storage stability of theradiation-sensitive resin composition, further improve the resolution ofthe resist, and prevent a change in line width of the resist pattern dueto a change in post-exposure delay (PED), so that a composition thatexhibits excellent process stability can be obtained. The acid diffusioncontroller (c) may be included in the radiation-sensitive resincomposition as a compound (described below) and/or may be included inthe polymer.

Examples of the acid diffusion controller (c) include amine compounds,amide group-containing compounds, urea compounds, nitrogen-containingheterocyclic compounds, and the like.

Examples of the amine compounds include mono(cyclo)alkylamines,di(cyclo)alkylamines, tri(cyclo)alkylamines, substituted-alkylanilinesor derivatives thereof, ethylenediamine,N,N,N′,N′-tetramethylethylenediamine, tetramethylenediamine,hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine,2,2-bis(4-aminophenyl)propane,2-(3-aminophenyl)-2-(4-aminophenyl)propane,2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane,2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane,1,4-bis[1-(4-aminophenyl)-1-methylethyl]benzene,1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene,bis(2-dimethylaminoethyl) ether, bis(2-diethylaminoethyl) ether,1-(2-hydroxyethyl)-2-imidazolizinone, 2-quinoxalinol,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine,N,N,N′,N″,N″-pentamethyldiethylenetriamine, and the like.

Examples of the amide group-containing compounds includeN-t-butoxycarbonyl group-containing amino compounds, N-t-amyloxycarbonylgroup-containing amino compounds, formamide, N-methylformamide,N,N-dimethylformamide, acetamide, N-methylacetamide,N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone,N-methylpyrrolidone, N-acetyl-1-adamantylamine, tris(2-hydroxyethyl)isocyanurate, and the like. Among these, N-t-butoxycarbonylgroup-containing amino compounds and N-t-amyloxycarbonylgroup-containing amino compounds are preferable, andN-t-butoxycarbonyl-4-hydroxypiperidine,N-t-amyloxycarbonyl-4-hydroxypiperidine, N-t-butoxycarbonylpyrrolidine,N-t-butoxycarbonyl-2-hydroxymethylpyrrolidine, andN-t-butoxycarbonyl-2-phenylbenzimidazole are more preferable.

Examples of the urea compounds include urea, methylurea,1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea,1,3-diphenylurea, tri-n-butylthiourea, and the like.

Examples of the nitrogen-containing heterocyclic compounds includeimidazoles, pyridines, piperazines, pyrazine, pyrazole, pyridazine,quinoxaline, purine, pyrrolidine, piperidine, piperidineethanol,3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine,1-(4-morpholinyl)ethanol, 4-acetylmorpholine,3-(N-morpholino)-1,2-propanediol, 1,4-dimethylpiperazine,1,4-diazabicyclo[2.2.2]octane, and the like.

A photodegradable base that generates a base upon exposure may be usedas the acid diffusion controller (c). Examples of the photodegradablebase include onium salt compounds that lose acid-diffusioncontrollability upon decomposition due to exposure. Examples of theonium salt compounds include sulfonium salt compounds shown by thefollowing formula (c1) and iodonium salt compounds shown by thefollowing formula (c2).

wherein R^(a) to R^(e) individually represent a hydrogen atom, an alkylgroup, an alkoxy group, a hydroxyl group, or a halogen atom, Z⁻ and E⁻represent OH⁻, R^(f)—COO⁻, or R^(f)—SO₃ ⁻, and R^(f) represents an alkylgroup, an aryl group, an alkaryl group, or an anion shown by thefollowing formula (d3).

wherein R²⁴ represents a linear or branched alkyl group having 1 to 12carbon atoms in which a part or all of the hydrogen atoms may besubstituted with a fluorine atom, or a linear or branched alkoxy grouphaving 1 to 12 carbon atoms, and u is an integer from 0 to 2.

Examples of the photodegradable base include the compounds shown by thefollowing formulas, and the like.

Among these, triphenylsulfonium salicylate, triphenylsulfonium10-camphorsulfonate, and triphenylsulfoniumN-butyltrifluoromethylsulfonamide are preferable.

These acid diffusion controllers (C) may be used either individually orin combination. The acid diffusion controller (D) is preferably used inan amount of less than 5 parts by mass based on 100 parts by mass of thepolymer (a1). If the amount of the acid diffusion controller (C) exceeds5 parts by mass, the sensitivity of the resulting resist may decrease.

Solvent (D)

The radiation-sensitive resin composition normally includes the solvent(D). The solvent is not particularly limited as long as the solvent candissolve the polymer (a1), the acid generator (B), and additionaloptional components. Examples of the solvent (D) include alcoholsolvents, ether solvents, ketone solvents, amide solvents, estersolvents, a mixture thereof, and the like.

Specific examples of the solvent (D) include the organic solventsmentioned above in connection with the step (4) of the resistpattern-forming method. Among these, propylene glycol monomethyl etheracetate, cyclohexanone, and γ-butyrolactone are preferable. Thesesolvents (D) may be used either individually or in combination.

Alicyclic Skeleton-Containing Compound

The alicyclic skeleton-containing compound improves the dry etchingresistance, the pattern shape, adhesion to a substrate, and the like.

Examples of the alicyclic skeleton-containing compound includeadamantane derivatives such as 1-adamantanecarboxylic acid,2-adamantanone, and t-butyl 1-adamantanecarboxylate; deoxycholates suchas t-butyl deoxycholate, t-butoxycarbonylmethyl deoxycholate, and2-ethoxyethyl deoxycholate; lithocholates such as t-butyl lithocholate,t-butoxycarbonylmethyl lithocholate, and 2-ethoxyethyl lithocholate;3-[2-hydroxy-2,2-bis(trifluoromethyl)ethyl]tetracyclo[4.4.0.1^(2.5).1^(7.1)]dodecane,2-hydroxy-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo[4.2.1.0^(3.7)]nonane,and the like. These alicyclic skeleton-containing compounds may be usedeither individually or in combination.

EXAMPLES

The invention is further described below by way of examples. Note thatthe invention is not limited to the following examples. The propertyvalues were measured by the following methods.

¹³C-NMR Analysis

The polymer was subjected to ¹³C-NMR analysis using a nuclear magneticresonance spectrometer (“JNM-EX270” manufactured by JEOL Ltd.).

Solid Content in Solution Containing Polysiloxane (A)

The solid content (mass %) in a solution containing the polysiloxane (A)was determined by baking 0.5 g of a solution containing the siloxane (A)at 250° C. for 30 minutes, and measuring the mass of the solid containedin the solution.

Synthesis of Polysiloxane (A)

The following silane compounds were used to synthesize the polysiloxane(A).

Silane compound (S−1): tetramethoxysilaneSilane compound (S-2): phenyltrimethoxysilaneSilane compound (S-3): 3-ethyl-3-oxetanylpropyltrimethoxysilaneSilane compound (S-4): methyltrimethoxysilaneSilane compound (S-5): 3-glycidyloxypropyltrimethoxysilaneSilane compound (S-6): 3-(trimethoxysilyl)propylsuccinic anhydrideSilane compound (S-7): 4-hydroxyphenyltrimethoxysilane

Synthesis Example 1 Synthesis of Polysiloxane (A−1)

1.28 g of oxalic acid was dissolved in 12.85 g of water with heating toprepare an oxalic acid aqueous solution. A flask charged with 25.05 g oftetramethoxysilane (silane compound (S−1)), 3.63 g ofphenyltrimethoxysilane (silane compound (S-2)), and 57.19 g of propyleneglycol monoethyl ether was fitted with a cooling tube and a droppingfunnel containing the oxalic acid aqueous solution. After heating themixture to 60° C. using an oil bath, the oxalic acid aqueous solutionwas slowly added dropwise to the mixture, and the mixture was reacted at60° C. for 4 hours. After completion of the reaction, the flaskcontaining the reaction solution was allowed to cool, and methanolproduced during the reaction was evaporated using an evaporator toobtain 97.3 g of a solution containing a polysiloxane (A−1). The solidcontent in the solution containing the polysiloxane (A−1) was 18.0 mass%. The Mw of the polysiloxane (A−1) was 2000.

Synthesis Example 2 Synthesis of Polysiloxane (A-2)

2.92 g of tetramethylammonium hydroxide (TMAH) was dissolved in 8.75 gof water with heating to prepare a TMAH aqueous solution. A flaskcharged with 11.67 g of the TMAH aqueous solution and 4.53 g of waterwas fitted with a cooling tube and a dropping funnel containing 10.65 gof tetramethoxysilane (silane compound (S−1)), 1.98 g ofphenyltrimethoxysilane (silane compound (S-2)), 2.72 g ofmethyltrimethoxysilane (silane compound (S-4)), and 20 g of methanol.After heating the mixture to 50° C. using an oil bath, the methanolsolution of the monomers was slowly added dropwise to the mixture, andthe mixture was reacted at 50° C. for 2 hours. After completion of thereaction, the flask containing the reaction solution was allowed tocool.

The reaction solution was added dropwise to 36.67 g of a methanolsolution of maleic acid that was prepared by dissolving 4.39 g of maleicanhydride in 16.14 g of water and 16.14 g of methanol, and the mixturewas stirred for 30 minutes. After the addition of 50 g of4-methyl-2-pentenone, the reaction solvent and methanol produced duringthe reaction were evaporated using an evaporator to obtain a4-methyl-2-pentenone solution of a polysiloxane. The solution was put ina separating funnel, washed with 80 g of water, and then washed with 40g of water. After the addition of 50 g of propylene glycol 1-ethyl etherto the 4-methyl-2-pentenone resin solution that had been transferred toa flask from the separating funnel, 4-methyl-2-pentenone was evaporatedusing an evaporator to obtain 51 g of a solution containing apolysiloxane (A-2). The solid content in the solution containing thepolysiloxane (A-2) was 18.0 mass %. The Mw of the polysiloxane (A-2) was4000.

Synthesis Examples 3 to 10 Synthesis of Polysiloxanes (A-3) to (A-10)

Polysiloxanes (A-3) to (A-10)) were synthesized in the same manner as inSynthesis Example 1, except that the silane compounds and the amountsthereof were changed as shown in Table 1. The solid content in thesolution containing the polysiloxane and the Mw of the polysiloxane areshown in Table 1.

TABLE 1 Silane compound Polysiloxane Amount Solid content (A) Type (mol%) Mw (mass %) Synthesis A-1 S-1 90 2000 18 Example 1 S-2 10 SynthesisA-2 S-1 70 4000 18 Example 2 S-2 10 S-4 20 Synthesis A-3 S-1 20 1600 18Example 3 S-3 80 Synthesis A-4 S-1 90 8400 18 Example 4 S-4 10 SynthesisA-5 S-1 70 1500 18 Example 5 S-2 5 S-4 25 Synthesis A-6 S-4 100 1800 18Example 6 Synthesis A-7 S-1 80 3000 18 Example 7 S-4 20 Synthesis A-8S-1 80 3000 18 Example 8 S-2 10 S-5 10 Synthesis A-9 S-1 80 3000 18Example 9 S-2 10 S-6 10 Synthesis A-10 S-1 80 3000 18 Example 10 S-4 10S-7 10

Preparation of Resist Underlayer Film-Forming Composition

The components (nitrogen-containing compound (B), acid generator (C),and solvent (D)) other than the polysiloxane (A) that were used toprepare the resist underlayer film-forming composition are listed below.

Nitrogen-Containing Compound (B)

B-1: N-t-amyloxycarbonyl-4-hydroxypiperidineB-2: N-t-butoxycarbonyl-4-hydroxypiperidine

Acid Generator (C)

C-1: triphenylsulfonium trifluoromethanesulfonateC-2: triphenylsulfoniumtricyclo[3.3.1.1^(3.7)]decanyldifluoromethanesulfonate

Solvent (D)

D-1: propylene glycol monoethyl ether acetateD-2: propylene glycol monoethyl etherD-3: propylene glycol monopropyl ether

Synthesis Example 11 Preparation of Resist Underlayer Film-FormingComposition (P−1)

9.70 parts by mass of the polysiloxane (A−1) and 0.05 parts by mass ofthe nitrogen-containing compound (B−1) were dissolved in 68.74 parts bymass of the solvent (D−1) and 21.51 parts by mass of the solvent (D-2).The solution was filtered through a filter having a pore size of 0.2 μmto obtain a resist underlayer film-forming composition (P−1).

Synthesis Examples 12 to 28 Preparation of Resist UnderlayerFilm-Forming Compositions (P-2) to (P-18)

Resist underlayer film-forming compositions (P-2) to (P-18) wereprepared in the same manner as in Synthesis Example 11, except that thecomponents and the amounts thereof were changed as shown in Table 2.Note that the symbol “-” in Table 2 indicates that the component was notused.

TABLE 2 Resist Solution of Nitrogen-containing Water underlayerpolysiloxane (A) compound (B) Acid generator (C) Solvent (D) Amountfilm-forming Amount Amount Amount Amount (parts composition Type (partsby mass) Type (parts by mass) Type (parts by mass) Type (parts by mass)by mass) Synthesis P-1 A-1 9.70 B-1 0.05 — — D-1/D-2 68.74/21.51 —Example 11 Synthesis P-2 A-1 9.70 B-2 0.05 — — D-1/D-2 68.74/21.51 —Example 12 Synthesis P-3 A-1 9.73 B-1 0.02 — — D-1/D-2 68.74/21.51 —Example 13 Synthesis P-4 A-2 9.70 B-1 0.05 — — D-1/D-2 68.74/21.51 —Example 14 Synthesis P-5 A-1/A-3 8.73/0.97 B-1 0.05 — — D-1/D-268.74/21.51 — Example 15 Synthesis P-6 A-1/A-4 9.21/0.49 B-1 0.05 — —D-1/D-2 68.74/21.51 — Example 16 Synthesis P-7 A-1/A-6 9.21/0.49 B-10.05 — — D-1/D-2/D-3 68.74/17.92/3.59 — Example 17 Synthesis P-8 A-5/A-69.21/0.49 B-1 0.05 — — D-2/D-3 72.33/17.92 — Example 18 Synthesis P-9A-6/A-7 0.49/9.21 B-1 0.05 — — D-1/D-2/D-3 68.74/17.92/3.59 — Example 19Synthesis P-10 A-1 9.75 — — — — D-1/D-2 68.74/21.51 — Example 20Synthesis P-11 A-8 9.75 — — — — D-2 90.25 — Example 21 Synthesis P-12A-9 9.75 — — — — D-1/D-2 36.10/54.15 — Example 22 Synthesis P-13 A-109.75 — — — — D-1/D-2 68.74/21.51 — Example 23 Synthesis P-14 A-1 9.73 —— C-1 0.02 D-1/D-2 36.10/54.15 — Example 24 Synthesis P-15 A-2 9.70 — —C-2 0.05 D-1/D-2 68.74/21.51 — Example 25 Synthesis P-16 A-1 9.68 B-10.05 C-1 0.02 D-1/D-2 36.10/54.15 — Example 26 Synthesis P-17 A-2 9.65B-1 0.05 C-2 0.05 D-1/D-2 68.74/21.51 — Example 27 Synthesis P-18 A-19.75 — — — — D-1/D-2 36.10/54.15 1.76 Example 28

Preparation of Radiation-Sensitive Resin Composition Synthesis ofPolymer (a1)

The following monomer compounds were used to synthesize the polymer(a1).

Synthesis Example 29 Synthesis of Polymer (a1-1)

12.9 g (50 mol %) of the compound (M-1) and 17.1 g (50 mol %) of thecompound (M-2) were dissolved in 60 g of methyl ethyl ketone, and 1.77 gof 2,2′-azobisisobutyronitrile (AIBN) was added to the solution toprepare a monomer solution. A three-necked flask (200 ml) charged with30 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, andheated to 80° C. with stirring. The monomer solution was added dropwiseto the flask over 3 hours using a dropping funnel. The monomers werepolymerized for 6 hours from the start of addition of the monomersolution. After completion of polymerization, the polymer solution wascooled with water to 30° C. or less, and poured into 600 g of methanol.A white powder that precipitated by this operation was filtered off. Thewhite powder was washed twice with 150 g of methanol in a slurry state,filtered off again, and dried at 50° C. for 17 hours to obtain a whitepowdery polymer (a1-1) (yield: 80%). The ratio of the content ofstructural units derived from the compound (M-1) to the content ofstructural units derived from the compound (M-2) in the polymer (a1-1)determined by ¹³C-NMR analysis was 49/51 (mol %). The polymer (a1-1) hadan Mw of 6900 and a dispersity (Mw/Mn) of 1.35.

Synthesis Example 30 Synthesis of Polymer (a1-2)

14.1 g (50 mol %) of the compound (M-3) and 15.9 g (50 mol %) of thecompound (M-2) were dissolved in 60 g of methyl ethyl ketone, and 0.5 gof AIBN was added to the solution to prepare a monomer solution. Athree-necked flask (200 ml) charged with 30 g of methyl ethyl ketone waspurged with nitrogen for 30 minutes, and heated to 80° C. with stirring.The monomer solution was added dropwise to the flask over 3 hours usinga dropping funnel. The monomers were polymerized for 6 hours from thestart of addition of the monomer solution. After completion ofpolymerization, the polymer solution was cooled with water to 30° C. orless, and poured into 600 g of methanol. A white powder thatprecipitated by this operation was filtered off. The white powder waswashed twice with 150 g of methanol in a slurry state, filtered offagain, and dried at 50° C. for 17 hours to obtain a white powderypolymer (a1-2) (yield: 76.5%). The ratio of the content of structuralunits derived from the compound (M-3) to the content of structural unitsderived from the compound (M-2) in the polymer (a1-2) determined by¹³C-NMR analysis was 48/52 (mol %). The polymer (a1-2) had an Mw of13,200 and a dispersity (Mw/Mn) of 1.53.

Synthesis Example 31 Synthesis of Polymer (a1-3)

11.1 g (40 mol %) of the compound (M-1), 3.9 g (10 mol %) of thecompound (M-4), 3.9 g (10 mol %) of the compound (M-6), and 11.2 g (40mol %) of the compound (M-5) were dissolved in 60 g of methyl ethylketone, and 1.3 g of AIBN was added to the solution to prepare a monomersolution. A three-necked flask (200 ml) charged with 30 g of methylethyl ketone was purged with nitrogen for 30 minutes, and heated to 80°C. with stirring. The monomer solution was added dropwise to the flaskover 3 hours using a dropping funnel. The monomers were polymerized for6 hours from the start of addition of the monomer solution. Aftercompletion of polymerization, the polymer solution was cooled with waterto 30° C. or less, and poured into 600 g of methanol. A white powderthat precipitated by this operation was filtered off. The white powderwas washed twice with 150 g of methanol in a slurry state, filtered offagain, and dried at 50° C. for 17 hours to obtain a white powderypolymer (a1-3) (Mw: 6400, Mw/Mn: 1.43, yield: 72.1%). The ratio of thecontent of structural units derived from the compound (M-1), the contentof structural units derived from the compound (M-4), the content ofstructural units derived from the compound (M-6), and the content ofstructural units derived from the compound (M-5) in the polymer (a1-3)was 38/10/11/41 (mol %).

Synthesis Example 32 Synthesis of Polymer (a1-4)

12.7 g (50 mol %) of the compound (M-1), 3.9 g (10 mol %) of thecompound (M-7), and 13.4 g (40 mol %) of the compound (M-2) weredissolved in 60 g of methyl ethyl ketone, and 1.2 g of AIBN was added tothe solution to prepare a monomer solution. A three-necked flask (200ml) charged with 30 g of methyl ethyl ketone was purged with nitrogenfor 30 minutes, and heated to 80° C. with stirring. The monomer solutionwas added dropwise to the flask over 3 hours using a dropping funnel.The monomers were polymerized for 6 hours from the start of addition ofthe monomer solution. After completion of polymerization, the polymersolution was cooled with water to 30° C. or less, and poured into 600 gof methanol. A white powder that precipitated by this operation wasfiltered off. The white powder was washed twice with 150 g of methanolin a slurry state, filtered off again, and dried at 50° C. for 17 hoursto obtain a white powdery polymer (a1-4) (Mw: 5900, Mw/Mn: 1.42, yield:72.3%). The ratio of the content of structural units derived from thecompound (M-1), the content of structural units derived from thecompound (M-7), and the content of structural units derived from thecompound (M-2) in the polymer (a1-4) was 48/11/41 (mol %).

Synthesis Example 33 Synthesis of Polymer (a1-5)

12.9 g (50 mol %) of the compound (M-1), 3.6 g (10 mol %) of thecompound (M-8), and 13.6 g (40 mol %) of the compound (M-2) weredissolved in 60 g of methyl ethyl ketone, and 1.3 g of AIBN was added tothe solution to prepare a monomer solution. A three-necked flask (200ml) charged with 30 g of methyl ethyl ketone was purged with nitrogenfor 30 minutes, and heated to 80° C. with stirring. The monomer solutionwas added dropwise to the flask over 3 hours using a dropping funnel.The monomers were polymerized for 6 hours from the start of addition ofthe monomer solution. After completion of polymerization, the polymersolution was cooled with water to 30° C. or less, and poured into 600 gof methanol. A white powder that precipitated by this operation wasfiltered off. The white powder was washed twice with 150 g of methanolin a slurry state, filtered off again, and dried at 50° C. for 17 hoursto obtain a white powdery polymer (a1-5) (Mw: 5700, Mw/Mn: 1.38, yield:72.5%). The ratio of the content of structural units derived from thecompound (M-1), the content of structural units derived from thecompound (M-8), and the content of structural units derived from thecompound (M-2) in the polymer (a1-5) was 49/11/40 (mol %).

Synthesis Example 340 Synthesis of Polymer (a1-6)

12.2 g (45 mol %) of the compound (M-3), 5.5 g (15 mol %) of thecompound (M-9), and 12.3 g (40 mol %) of the compound (M-2) weredissolved in 60 g of methyl ethyl ketone, and 0.5 g of AIBN was added tothe solution to prepare a monomer solution. A three-necked flask (200ml) charged with 30 g of methyl ethyl ketone was purged with nitrogenfor 30 minutes, and heated to 80° C. with stirring. The monomer solutionwas added dropwise to the flask over 3 hours using a dropping funnel.The monomers were polymerized for 6 hours from the start of addition ofthe monomer solution. After completion of polymerization, the polymersolution was cooled with water to 30° C. or less, and poured into 600 gof methanol. A white powder that precipitated by this operation wasfiltered off. The white powder was washed twice with 150 g of methanolin a slurry state, filtered off again, and dried at 50° C. for 17 hoursto obtain a white powdery polymer (a1-6) (Mw: 13,400, Mw/Mn: 1.59,yield: 76.3%). The ratio of the content of structural units derived fromthe compound (M-13), the content of structural units derived from thecompound (M-19), and the content of structural units derived from thecompound (M-12) in the polymer (a1-6) was 44/15/41 (mol %).

Synthesis of Polymer (a2)

The following monomer compounds were used to synthesize the polymer(a2).

Synthesis Example 35 Synthesis of Polymer (a2-1)

10.4 g (30 mol %) of the compound (M-10) and 19.6 g (70 mol %) of thecompound (M-11) were dissolved in 60 g of methyl ethyl ketone, and 0.91g (5 mol %) of 2,2′-azobis(isobutyronitrile) was added to the solutionto prepare a monomer solution. A three-necked flask (200 ml) chargedwith 30 g of methyl ethyl ketone was purged with nitrogen for 30minutes, and heated to 80° C. with stirring. The monomer solution wasadded dropwise to the flask over 3 hours using a dropping funnel. Themonomers were polymerized for 6 hours from the start of addition of themonomer solution. After completion of polymerization, the polymersolution was cooled with water to 30° C. or less, and poured into 600 gof methanol. A white powder that precipitated by this operation wasfiltered off. The white powder was washed twice with 150 g of methanolin a slurry state, filtered off again, and dried at 50° C. for 12 hoursto obtain a white powdery polymer (a2-1) (Mw: 5900, Mw/Mn: 1.58, yield:68%). The ratio of the content of structural units derived from thecompound (M-10) to the content of structural units derived from thecompound (M-11) in the polymer (a2-1) was 31/69 (mol %).

Synthesis Example 36 Synthesis of Polymer (a2-2)

35.8 g (70 mol %) of the compound (M-12) and 14.2 g (30 mol %) of thecompound (M-13) were dissolved in 100 g of methyl ethyl ketone, and 3.2g of dimethyl 2,2′-azobisisobutyrate (initiator) was added to thesolution to prepare a monomer solution. A 500 ml three-necked flask wascharged with 100 g of methyl ethyl ketone, purged with nitrogen for 30minutes, and heated to 80° C. with stirring. The monomer solution wasadded dropwise to the flask over 3 hours using a dropping funnel. Themonomers were polymerized for 6 hours from the start of addition of themonomer solution. After completion of polymerization, the polymersolution was cooled to 30° C. or less, and washed with 825 g of amethanol/methyl ethyl ketone/hexane mixed solution (2/1/8 (mass ratio)).The solvent was replaced with propylene glycol methyl ether acetate toobtain a solution of a polymer 8 (38.0 g (solid content), yield: 76.0%).The ratio of the content of structural units derived from the compound(M-12) to the content of structural units derived from the compound(M-13) in the polymer (a2-2) determined by ¹³C-NMR analysis was 70/30(mol %). The polymer (a2-2) had an Mw of 7000 and a dispersity (Mw/Mn)of 1.40.

The components (acid generator (b), acid diffusion controller (c), andsolvent (d)) other than the polymers (a1) and (a2)) that were used toprepare the radiation-sensitive resin composition are listed below.

Acid Generator (b)

b-1: triphenylsulfonium1,1,2,2-tetrafluoro-6-(1-adamantanecarbonyloxy)hexane-1-sulfonate(compound shown by the following formula (b-1))b-2: 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate(compound shown by the following formula (b-2))b-3: triphenylsulfonium 2-(1-adamantyl)-1,1-difluoroethanesulfonate(compound shown by the following formula (b-3))

Acid Diffusion Controller (c)

c-1: triphenylsulfonium salicylate (compound shown by the followingformula (c-1))c-2: N-t-amyloxycarbonyl-4-hydroxypiperidine (compound shown by thefollowing formula (c-2))c-3: N-t-butoxycarbonyl-4-hydroxypiperidine (compound shown by thefollowing formula (c-3))c-4: triphenylsulfonium 10-camphorsulfonate (compound shown by thefollowing formula (c-4))c-5: N-t-butoxycarbonylpyrrolidine (compound shown by the followingformula (c-5))c-6: N-t-butoxycarbonyl-2-phenylbenzimidazole (compound shown by thefollowing formula (c-6))c-7: N-t-butoxycarbonyl-2-hydroxymethylpyrrolidine (compound shown bythe following formula (c-7))c-8: triphenylsulfonium N-butyltrifluoromethylsulfonamide (compoundshown by the following formula (c-8))

Solvent (d)

d-1: propylene glycol monoethyl ether acetated-2: cyclohexanoned-3: γ-butyrolactone

Synthesis Example 37 Preparation of Radiation-Sensitive ResinComposition (J−1)

100 parts of the polymer (a1-1), 3 parts of the polymer (a2-1), 10.8parts of the acid generator (b−1), 4.3 parts of the acid diffusioncontroller (c−1), 2185 parts of the solvent (d−1), 935 parts of thesolvent (d-2), and 30 parts of the solvent (d-3) were mixed to obtain aradiation-sensitive resin composition (J−1).

Synthesis Examples 38 to 50 Preparation of Radiation-Sensitive ResinCompositions (J-2) to (J-14)

Radiation-sensitive resin compositions (J-2) to (J-14) were prepared inthe same manner as in Synthesis Example 37, except that the componentsand the amounts thereof were changed as shown in Table 3.

TABLE 3 Radiation- Polymer (a2) Acid diffusion sensitive Polymer (a1)Amount Acid generator (B) controller (C) Solvent (D) resin Amount (partsAmount Amount Amount composition Type (parts by mass) Type by mass) Type(parts by mass) Type (parts by mass) Type (parts by mass) Synthesis J-1a1-1 100 a2-1 3 b-1 10.8 c-1 4.3 d-1/d-2/d-3 2185/935/30 Example 37Synthesis J-2 a1-1 100 a2-2 3 b-3 8.5 c-2 1.7 d-1/d-2/d-3 2200/950/30Example 38 Synthesis J-3 a1-1 100 a2-2 3 b-3 8.5 c-4 5.4 d-1/d-2/d-32200/950/30 Example 39 Synthesis J-4 a1-2 100 a2-2 3 b-3 8.0 c-2 0.9d-1/d-2/d-3 2200/950/30 Example 40 Synthesis J-5 a1-2 100 a2-2 3 b-3 8.0c-4 2.1 d-1/d-2/d-3 2200/950/30 Example 41 Synthesis J-6 a1-2 100 a2-2 3b-3 8.0 c-8 2.1 d-1/d-2/d-3 2200/950/30 Example 42 Synthesis J-7 a1-3100 a2-1 3 b-2 9.6 c-3 1.2 d-1/d-2/d-3 2200/950/30 Example 43 SynthesisJ-8 a1-3 100 a2-1 3 b-2 9.6 c-6 1.7 d-1/d-2/d-3 2200/950/30 Example 44Synthesis J-9 a1-4 100 a2-1 3 b-2 9.6 c-5 1.0 d-1/d-2/d-3 2200/950/30Example 45 Synthesis J-10 a1-4 100 a2-1 3 b-2 9.6 c-7 1.3 d-1/d-2/d-32200/950/30 Example 46 Synthesis J-11 a1-4 100 a2-2 3 b-1 10.0 c-5 1.0d-1/d-2/d-3 2200/950/30 Example 47 Synthesis J-12 a1-4 100 a2-1 3 b-110.0 c-7 1.2 d-1/d-2/d-3 2200/950/30 Example 48 Synthesis J-13 a1-5 100a2-2 3 b-3 8.0 c-4 2.1 d-1/d-2/d-3 2200/950/30 Example 49 Synthesis J-14a1-6 100 a2-2 3 b-3 8.0 c-4 2.1 d-1/d-2/d-3 2200/950/30 Example 50

Evaluation of Properties of Resist Underlayer Film

A resist underlayer film was formed by the following method using theresist underlayer film-forming composition ((P−1) to (P-18)), and theproperties of the resist underlayer film were evaluated as describedbelow.

Formation of Resist Underlayer Film

The resist underlayer film-forming composition (P−1) obtained inSynthesis Example 11 was spin-coated onto a silicon wafer using acoater/developer (“CLEAN TRACK ACT 12” manufactured by Tokyo ElectronLtd.) (hereinafter the same unless otherwise specified). The resultingfilm was prebaked (PB) at 220° C. for 1 minute using a hot plate to forma resist underlayer film. The thickness of the resist underlayer filmmeasured using a film thickness meter (“M-2000D” manufactured by J. A.Woollam) was 30 nm.

Evaluation of Properties

The substrate reflectivity, the residual resist amount, and the oxygenashing resistance of the resist underlayer film were evaluated by thefollowing methods using the radiation-sensitive resin composition (J−1)obtained in Synthesis Example 37.

Substrate Reflectivity

The refractive index parameter (n) and the extinction coefficient (k) ofthe resist underlayer film, an antireflective film formed using anantireflective film-forming material (“NFC HM8006” manufactured by JSRCorporation), and a resist film formed using the radiation-sensitiveresin composition were measured using a high-speed spectroscopicellipsometer (“M-2000” manufactured by J. A. Woollam). The substratereflectivity (NA: 1.3, Dipole) of a stacked film of the resist film, theresist underlayer film, and the antireflective film was calculated fromthe measured values using simulation software (“Prolith” manufactured byKLA-Tencor). A case where the substrate reflectivity was 1% or less wasevaluated as “A”, a case where the substrate reflectivity was more than1% and 2% or less was evaluated as “B”, and a case where the substratereflectivity was more than 2% was evaluated as “C”. The evaluationresults are shown in Table 4.

Residual Resist Amount

The radiation-sensitive resin composition was spin-coated onto theresist underlayer film, and prebaked (PB) at 100° C. for 60 seconds on ahot plate to form a resist film having a thickness of 100 nm. Afterdeveloping the resist film for 1 minute using butyl acetate, thethickness of the film (resist underlayer film+residual resist film) onthe substrate was measured. The thickness of the film was measured usinga film thickness meter (“M-2000D” manufactured by J. A. Woollam)(hereinafter the same). The difference between the thickness of theresist underlayer film before development using the organic solvent andthe thickness of the film after development was calculated, and taken asthe residual resist amount (nm). The results are shown in Table 4. Acase where the residual resist amount was less than 5 nm was evaluatedas “A”, and a case where the residual resist amount was 5 nm or more wasevaluated as “B”.

Oxygen Ashing Resistance

The resist underlayer film was subjected to an O₂ treatment at 100 W for120 seconds using an ashing system (“NA1300” manufactured by ULVAC). Thedifference between the thickness of the resist underlayer film beforethe O₂ treatment and the thickness of the resist underlayer film afterthe O₂ treatment was calculated to evaluate the oxygen ashingresistance. The results are shown in Table 4. A case where thedifference was less than 5 nm was evaluated as “A”, a case where thedifference was 5 nm or more and 8 nm or less was evaluated as “B”, and acase where the difference was more than 8 nm was evaluated as “C”.

Formation of Resist Pattern Examples 1 to 18

A contact hole pattern (i.e., hole pattern) and a line-and-space pattern(i.e., trench pattern) were formed by the following method using theresist underlayer film-forming composition ((P−1) to (P-18)) and theradiation-sensitive resin composition (J−1) shown in Table 4, andevaluated as described below. The evaluation results are shown in Table4.

Formation of Contact Hole Pattern

An antireflective film-forming material (“HM8006” manufactured by JSRCorporation) was spin-coated onto a 12-inch silicon wafer, and prebaked(PB) (250° C., 60 seconds) to obtain an antireflective film having athickness of 100 nm. The resist underlayer film-forming composition(P−1) was spin-coated onto the antireflective film, prebaked (PB) (220°C., 60 seconds), and cooled (23° C., 60 seconds) to form a resistunderlayer film having a thickness of 30 nm. The radiation-sensitiveresin composition (J−1) was spin-coated onto the resist underlayer film,prebaked (PB) (90° C., 60 seconds), and cooled (23° C., 30 seconds) toform a resist film having a thickness of 100 nm.

The resist film was subjected to reduced projection exposure through amask (220 nm dot/440 nm pitch) using an ArF immersion scanner (“S610C”manufactured by Nikon Corporation) (NA: 1.30, Quadrupole). The resistfilm was subjected to PEB (105° C., 60 seconds) on the hot plate of acoater/developer (“CLEAN TRACK Lithius Pro-i” manufactured by TokyoElectron Ltd.), cooled (23° C., 30 seconds), subjected to puddledevelopment (30 seconds) using butyl acetate as the developer utilizingthe development cup of a coater/developer (“CLEAN TRACK ACT 12”manufactured by Tokyo Electron Ltd.), and rinsed withmethylisobutylcarbinol (MIBC). The wafer was spin-dried at 2000 rpm for15 seconds to obtain a test substrate on which a 55 nm hole/110 nm pitchresist pattern was formed.

Evaluation

The minimum hole dimension, the CDU, and the pattern shape wereevaluated by the following methods using the test substrate on which thecontact hole pattern was formed. The resist pattern on the testsubstrate was measured and observed using a scanning electron microscope(“CG-4000” manufactured by Hitachi High-Technologies Corporation).

Minimum Hole Dimension

A dose (mJ/cm²) at which a resist pattern having a hole diameter of 55nm and a hole-to-hole distance (space) of 55 nm was formed wasdetermined to be an optimum dose. The exposure step was performed whileincreasing the dose stepwise at a value higher than the optimum dose. Inthis case, since the diameter of the hole gradually decreases, a hole isnot formed at a given dose. A hole size corresponding to the maximumdose at which a hole pattern was formed was defined as the minimum holedimension (nm), and used as an index of the resolution.

CDU

The diameter of the hole (diameter: 55 nm) formed at the optimum dosewas measured at an arbitrary 24 points. The 3σ value that indicates thedistribution of the measured values was calculated, and taken as theCDU. A case where the 3G value was less than 2 nm was evaluated as “A”,a case where the 3σ value was 2 nm or more and 3.5 nm or less wasevaluated as “B”, and a case where the 3σ value was more than 3.5 nm wasevaluated as “C”.

Pattern Shape

The cross-sectional shape of a 55 nm hole/110 nm pitch hole patternformed using the resist film formed on the substrate was observed(measured) using a scanning electron microscope (“S-4800” manufacturedby Hitachi High-Technologies Corporation). The hole diameter Lb at thebottom of the resist pattern and the hole width La at the top of theresist pattern were measured. A case where “0.9<(La/Lb)<1.1” wassatisfied was evaluated as “A”, and a case where “0.9<(La/Lb)<1.1” wasnot satisfied was evaluated as “B”.

Formation of Line-and-Space Pattern

An antireflective film-forming material (“HM8006” manufactured by JSRCorporation) was spin-coated onto a 12-inch silicon wafer, and prebaked(PB) (250° C., 60 seconds) to obtain an antireflective film having athickness of 100 nm. The resist underlayer film-forming composition(P−1) was spin-coated onto the antireflective film, prebaked (PB) (220°C., 60 seconds), and cooled (23° C., 60 seconds) to form a resistunderlayer film having a thickness of 30 nm. The radiation-sensitiveresin composition (J−1) was spin-coated onto the resist underlayer film,prebaked (PB) (90° C., 60 seconds), and cooled (23° C., 30 seconds) toform a resist film having a thickness of 100 nm.

The resist layer was subjected to reduced projection exposure through amask (40 nm line/80 nm pitch) using an ArF immersion scanner (“S610C”manufactured by Nikon Corporation) (NA: 1.30, Dipole). The resist filmwas subjected to PEB (100° C., 60 seconds) on the hot plate of thecoater/developer (“CLEAN TRACK Lithius Pro-i”), cooled (23° C., 30seconds), subjected to puddle development (30 seconds) using butylacetate as the developer, and rinsed with MIBC. The wafer was spin-driedat 2000 rpm for 15 seconds to obtain a test substrate on which a 40 nmline/80 nm pitch resist pattern was formed.

Evaluation

The minimum pre-collapse dimension and the pattern shape were evaluatedby the following methods using the test substrate. The resist pattern onthe test substrate was measured and observed using a scanning electronmicroscope (“CG-4000” manufactured by Hitachi High-TechnologiesCorporation).

Minimum Pre-Collapse Dimension

A dose (mJ/cm²) at which a resist pattern having a line width of 40 nmand a line-to-line distance (space) of 40 nm was formed was determinedto be an optimum dose. The exposure step was performed while increasingthe dose stepwise at a value lower than the optimum dose. In this case,since the line width of the pattern gradually decreases, the resistpattern collapses when the resist pattern has a line width correspondingto a given dose. A line width corresponding to the maximum dose at whichthe resist pattern did not collapse was defined as the minimumpre-collapse dimension (nm), and used as an index of the patterncollapse resistance.

Pattern Shape

A case where the bottom of the resist pattern was not footed wasevaluated as “A”, and a case where pattern collapse or footing occurredwas evaluated as “B”.

TABLE 4 Lithographic evaluation Property evaluation Line-and-spaceevaluation Resist Residual Oxygen Contact hole evaluation Minimumunderlayer Radiation- resist ashing Minimum hole pre-collapsefilm-forming sensitive Substrate amount resistance dimension CDUdimension composition resin composition reflectivity (nm) (nm) (nm) (nm)Pattern shape (nm) Pattern shape Example 1 P-1 J-1 A <1 3 45 1.9 A 42 AExample 2 P-2 J-1 A <1 3 45 1.9 A 42 A Example 3 P-3 J-1 A <1 3 45 1.9 A36 A Example 4 P-4 J-1 A <1 3 45 1.9 A 38 A Example 5 P-5 J-1 A <1 5 482.8 A 40 A Example 6 P-6 J-1 A <1 3 45 2.5 A 36 A Example 7 P-7 J-1 A <15 48 3.0 A 40 A Example 8 P-8 J-1 A <1 5 48 3.5 A 40 A Example 9 P-9 J-1A <1 5 48 3.5 A 42 A Example 10 P-10 J-1 A <1 7 45 1.8 A 34 A Example 11P-11 J-1 A <1 7 45 1.8 A 32 A Example 12 P-12 J-1 A <1 7 45 1.8 A 32 AExample 13 P-13 J-1 B <1 7 45 1.9 A 34 A Example 14 P-14 J-1 A <1 8 451.9 A 32 A Example 15 P-15 J-1 A <1 8 45 2.0 A 32 A Example 16 P-16 J-1A <1 5 45 2.0 A 34 A Example 17 P-17 J-1 A <1 5 45 2.0 A 34 A Example 18P-18 J-1 A <1 5 45 2.0 A 34 A

As is clear from the results shown in Table 4, a contact hole patternthat exhibited excellent resolution, CDU, and pattern shape, and aline-and-space pattern that exhibited excellent pattern collapseresistance and pattern shape could be formed using the resistpattern-forming method according to one embodiment of the invention.Moreover, the substrate reflectivity, the residual resist amount, andthe oxygen ashing resistance were good when using the resistpattern-forming method.

Matching Between Resist Underlayer Film-Forming Composition andRadiation-Sensitive Resin Composition

A lithographic performance matching test was performed using eachcombination of the resist underlayer film-forming composition and theradiation-sensitive resin composition shown in Table 5. A resistunderlayer film and a resist film were formed, and a contact holepattern or a line-and-space pattern was formed as described below. Eachpattern was evaluated as described below. The results are shown in Table5.

Examples 19 to 38 Formation of Resist Underlayer Film and Resist Film

An antireflective film and a resist underlayer film were formed on a12-inch silicon wafer in the same manner as in Examples 1 to 18. Theradiation-sensitive resin composition (see Table 5) was spin-coated ontothe resist underlayer film using the coater/developer “CLEAN TRACK ACT12”, and prebaked (PB) at 80° C. for 60 seconds on a hot plate to form aresist film having a thickness of 0.10 μm.

Formation of Contact Hole Pattern

The resist layer was subjected to reduced projection exposure through amask (216 nm dot/416 nm pitch) and water using an ArF immersion scanner(“S610C” manufactured by Nikon Corporation) (NA: 1.30, Quadrupole). Theresist film was subjected to PEB at the temperature shown in Table 5 for60 seconds, developed at 23° C. for 30 seconds using n-butyl acetate asthe developer, rinsed with MIBC for 10 seconds, and dried to form acontact hole pattern. An optimum dose at which a 60 nm hole/104 nm pitchhole pattern was formed on the wafer was determined to be an optimumdose, and taken as the sensitivity (mJ/cm²).

Evaluation

The depth of focus, the CDU, the minimum hole dimension, and the patternshape were evaluated by the following methods using the contact holepattern.

Depth of Focus (DOF)

A DOF at which the size of the contact hole pattern formed using theresist film formed on the substrate at the optimum dose was within ±10%with respect to a 60 nm hole/104 nm pitch pattern and a 60 nm hole/800nm pitch pattern was determined, and a common DOF region was determinedto be the DOF (m). The dimensions of the hole pattern were measured fromabove using a scanning electron microscope (“CG4000” manufactured byHitachi High-Technologies Corporation). The DOF measurement results areshown in Table 5.

CDU

The diameter of the hole of the 60 nm hole pattern formed using theresist film formed on the substrate was measured at an arbitrary 24points, and the 36 value that indicates the distribution was taken asthe CDU. The results are shown in Table 5.

Minimum Hole Dimension

The resist film was subjected to reduced projection exposure throughwater using a dot pattern that was designed so that the pattern pitchafter reduced projection exposure became 104 nm (diameter), and theminimum hole dimension was measured while increasing the dose. Theresults are shown in Table 5.

Pattern Shape

The cross-sectional shape of a 60 nm hole/104 nm pitch hole patternformed using the resist film formed on the substrate was observed(measured) using a scanning electron microscope (“S-4800” manufacturedby Hitachi High-Technologies Corporation). The hole diameter Lb at thebottom of the resist pattern and the hole width La at the top of theresist pattern were measured. A case where “0.9<(La/Lb)<1.1” wassatisfied was evaluated as “A”, and a case where “0.9<(La/Lb)<1.1” wasnot satisfied was evaluated as “B”.

Formation of Line-and-Space Pattern

The resist layer was subjected to reduced projection exposure through amask (40 nm line/80 nm pitch) using an ArF immersion scanner (“S610C”manufactured by Nikon Corporation) (NA: 1.30, Dipole). The resist filmwas subjected to PEB at the temperature shown in Tables 5 to 7 for 60seconds on the hot plate of the coater/developer (“CLEAN TRACK LithiusPro-i”), cooled (23° C., 30 seconds), subjected to puddle development(30 seconds) using butyl acetate as the developer, and rinsed with MIBC.The wafer was spin-dried at 2000 rpm for 15 seconds to obtain a testsubstrate on which a 40 nm line/80 nm pitch resist pattern was formed.

The minimum pre-collapse dimension and the pattern shape were evaluatedusing the test substrate. The resist pattern on the test substrate wasmeasured and observed using a scanning electron microscope (“CG-4000”manufactured by Hitachi High-Technologies Corporation).

Minimum Pre-Collapse Dimension

The minimum pre-collapse dimension (nm) was measured in the same manneras in Examples 1 to 18, and used as an index of the pattern collapseresistance. The minimum pre-collapse dimension measurement results areshown in Table 5.

Pattern Shape

A case where the bottom of the resist pattern was not footed wasevaluated as “A”, and a case where pattern collapse or footing occurredwas evaluated as “B”.

When Using Another Developer

Each item was evaluated in the same manner as described above, exceptthat methyl n-pentyl ketone or anisole was used as the developer insteadof n-butyl acetate. The evaluation results obtained when using methyln-pentyl ketone as the developer are shown in Table 6, and theevaluation results obtained when using anisole as the developer areshown in Table 7.

Comparative Examples 1 to 4 Formation of Resist Underlayer Film andResist Film

A resist film was formed on a resist underlayer film in the same manneras in Examples 19 to 39, except that the radiation-sensitive resincomposition shown in Table 5 was used.

Formation and Evaluation of Contact Hole Pattern and Line-and-SpacePattern

A contact hole pattern and a line-and-space pattern were formed in thesame manner as in Examples 19 to 39, except that the PEB temperatureshown in Table 5 was employed, and a 2.38 mass % tetramethylammoniumhydroxide aqueous solution was used as the developer. The resultingpattern was evaluated in the same manner as in Examples 19 to 39. Theevaluation results are shown in Table 5. Note that the contact holepattern could not be resolved in Comparative Examples 1 to 4. The symbol“-” in Table 5 indicates that the corresponding evaluation was notperformed.

TABLE 5 Lithographic evaluation (developer: butyl acetate) ResistRadiation- Contact hole evaluation Line-and-space evaluation underlayersensitive PEB Minimum Minimum film-forming resin temperature SensitivityDOF CDU hole Pattern Sensitivity pre-collapse Pattern compositioncomposition (° C.) (mJ/cm²) (μm) (nm) dimension (nm) shape (mJ/cm²)dimension (nm) shape Example 19 P-10 J-2 105 13.5 0.10 1.7 44 A 46.0 36A Example 20 P-10 J-3 105 14.0 0.10 1.6 44 A 47.5 37 A Example 21 P-10J-4 85 12.5 0.12 1.7 43 A 42.5 34 A Example 22 P-10 J-5 85 10.5 0.12 1.642 A 35.5 35 A Example 23 P-10 J-6 85 10.5 0.12 1.6 42 A 36.0 35 AExample 24 P-10 J-7 100 10.0 0.08 2.1 47 A 34.0 38 A Example 25 P-10 J-8105 10.5 0.08 2.2 46 A 35.0 38 A Example 26 P-10 J-9 105 10.5 0.08 2.147 A 36.0 39 A Example 27 P-10 J-10 105 10.5 0.08 2.2 46 A 36.0 39 AExample 28 P-10 J-11 105 11.5 0.08 2.0 46 A 39.0 38 A Example 29 P-10J-12 105 11.5 0.10 1.9 46 A 39.0 38 A Example 30 P-10 J-13 85 11.0 0.101.7 43 A 37.5 37 A Example 31 P-10 J-14 105 11.5 0.08 1.6 42 A 39.0 35 AExample 32 P-1 J-2 105 12.5 0.10 1.8 44 A 42.5 40 A Example 33 P-1 J-485 12.5 0.12 1.8 43 A 42.5 37 A Example 34 P-1 J-7 100 10.0 0.08 2.2 47A 34.0 42 A Example 35 P-1 J-14 105 11.5 0.08 1.7 42 A 39.0 39 A Example36 P-16 J-2 105 12.5 0.10 1.9 44 A 42.5 36 A Example 37 P-16 J-4 85 12.50.12 1.9 43 A 42.5 34 A Example 38 P-16 J-7 100 10.0 0.08 2.3 47 A 34.038 A Example 39 P-16 J-14 105 11.5 0.08 1.8 42 A 39.0 35 A ComparativeP-10 J-2 105 Could not be — — — — 38.5 39 B Example 1 resolvedComparative P-10 J-4 85 Could not be — — — — 38.5 39 B Example 2resolved Comparative P-10 J-7 100 Could not be — — — — 30.5 40 B Example3 resolved Comparative P-10 J-14 105 Could not be — — — — 35.0 39 BExample 4 resolved

TABLE 6 Lithographic evaluation (developer: methyl n-pentyl ketone)Contact hole evaluation Line-and-space evaluation Resist Radiation-Minimum Minimum underlayer sensitive PEB hole pre-collapse film-formingresin temperature Sensitivity DOF CDU dimension Sensitivity dimensioncomposition composition (° C.) (mJ/cm²) (μm) (nm) (nm) Pattern shape(mJ/cm²) (nm) Pattern shape Example 19 P-10 J-2 105 21.5 0.10 1.5 40 A73.0 31 A Example 20 P-10 J-3 105 22.0 0.10 1.4 40 A 75.0 31 A Example21 P-10 J-4 85 20.0 0.12 1.5 39 A 68.0 29 A Example 22 P-10 J-5 85 16.50.12 1.4 38 A 56.0 30 A Example 23 P-10 J-6 85 16.0 0.12 1.4 38 A 55.030 A Example 24 P-10 J-7 100 15.5 0.08 1.9 42 A 53.0 32 A Example 25 P-1J-8 105 16.0 0.08 2.0 41 A 55.0 32 A Example 26 P-10 J-9 105 16.5 0.081.9 42 A 56.0 33 A Example 27 P-16 J-10 105 16.0 0.08 2.0 41 A 55.0 33 AExample 28 P-16 J-11 105 18.0 0.08 1.8 41 A 60.0 32 A Example 29 P-10J-12 105 17.5 0.10 1.7 41 A 60.0 32 A Example 30 P-10 J-13 85 18.0 0.101.5 39 A 61.0 31 A Example 31 P-10 J-14 105 17.5 0.08 1.4 38 A 59.0 30 AExample 32 P-1 J-2 105 20.0 0.10 1.6 40 A 68.0 34 A Example 33 P-1 J-485 20.0 0.12 1.6 39 A 68.0 32 A Example 34 P-1 J-7 100 15.5 0.08 2.0 42A 53.0 36 A Example 35 P-1 J-14 105 17.5 0.08 1.5 38 A 59.0 33 A Example36 P-16 J-2 105 20.0 0.10 1.7 40 A 68.0 31 A Example 37 P-16 J-4 85 20.00.12 1.7 39 A 68.0 29 A Example 38 P-16 J-7 100 15.5 0.08 2.1 42 A 53.032 A Example 39 P-16 J-14 105 17.5 0.08 1.6 38 A 59.0 30 A

TABLE 7 Lithographic evaluation (developer: anisole) Contact holeevaluation Line-and-space evaluation Resist Radiation- Minimum Minimumunderlayer sensitive PEB hole pre-collapse film-forming resintemperature Sensitivity DOF CDU dimension Sensitivity dimensioncomposition composition (° C.) (mJ/cm²) (μm) (nm) (nm) Pattern shape(mJ/cm²) (nm) Pattern shape Example 19 P-10 J-2 105 17.5 0.10 1.6 42 A60.0 34 A Example 20 P-10 J-3 105 18.0 0.10 1.5 42 A 61.0 35 A Example21 P-10 J-4 85 16.5 0.12 1.6 41 A 55.0 32 A Example 22 P-10 J-5 85 13.50.12 1.5 40 A 45.0 33 A Example 23 P-10 J-6 85 13.0 0.12 1.5 40 A 45.033 A Example 24 P-10 J-7 100 12.5 0.08 2.0 45 A 43.0 36 A Example 25P-10 J-8 105 13.0 0.08 2.1 44 A 43.0 36 A Example 26 P-10 J-9 105 13.50.08 2.0 45 A 46.0 37 A Example 27 P-10 J-10 105 13.0 0.08 2.1 44 A 45.037 A Example 28 P-10 J-11 105 14.5 0.08 1.9 44 A 49.0 36 A Example 29P-10 J-12 105 14.0 0.10 1.8 44 A 48.0 36 A Example 30 P-10 J-13 85 14.50.10 1.6 41 A 48.0 35 A Example 31 P-10 J-14 105 14.0 0.08 1.5 40 A 48.033 A Example 32 P-1 J-2 105 16.5 0.10 1.7 42 A 56.0 38 A Example 33 P-1J-4 85 16.5 0.12 1.7 41 A 56.0 36 A Example 34 P-1 J-7 100 12.5 0.08 2.145 A 43.0 40 A Example 35 P-1 J-14 105 14.0 0.08 1.6 40 A 48.0 37 AExample 36 P-16 J-2 105 16.5 0.10 1.8 42 A 56.0 34 A Example 37 P-16 J-485 16.5 0.12 1.8 41 A 56.0 32 A Example 38 P-16 J-7 100 12.5 0.08 2.2 45A 43.0 36 A Example 39 P-16 J-14 105 14.0 0.08 1.7 40 A 48.0 33 A

As is clear from the results shown in Tables 5 to 7, the resistpattern-forming method according to one embodiment of the inventioncould form a contact hole pattern and a line-and-space pattern thatexhibited an excellent DOF, CDU, resolution, pattern collapseresistance, and pattern shape when using an ester, ketone, or etherorganic solvent as the developer. A contact hole pattern could not beresolved when using an alkaline developer. The line-and-space patternobtained using an alkaline developer exhibited poor pattern collapseresistance and a poor pattern shape as compared with the case where anorganic solvent was used as the developer.

Formation of Contact Hole Pattern Utilizing a Plurality of ExposureSteps

Matching between the resist underlayer film-forming composition and theradiation-sensitive resin composition was evaluated when forming acontact hole pattern utilizing a plurality of exposure steps. A contacthole pattern was formed by the following method using each combinationof the resist underlayer film-forming composition and theradiation-sensitive resin composition shown in Table 8. The results areshown in Table 8.

Examples 40 to 47 Formation of Contact Hole Pattern

A resist underlayer film and a resist film were formed in the samemanner as in Examples 19 to 39. The resist film was exposed through amask (40 nm line/80 nm pitch) using an ArF immersion scanner(“NSR-S610C” manufactured by Nikon Precision Inc.) (NA: 1.3, Dipole Y).In this case, the resist film was subjected to a first reducedprojection exposure at a dose (sensitivity) at which a 40 nm line/80 nmpitch pattern was formed, and subjected to a second reduced projectionexposure (NA: 1.3, Dipole X) at an identical dose so that the linesformed by the first reduced projection exposure intersected the linesformed by the second reduced projection exposure. The resist film wassubjected to PEB at the temperature shown in Table 8 for 60 seconds onthe hot plate of the coater/developer (“CLEAN TRACK Lithius Pro-i”),cooled (23° C., 30 seconds), subjected to puddle development (30seconds) using n-butyl acetate as the developer, and rinsed (7 seconds)with MIBC. The wafer was spin-dried at 2000 rpm for 15 seconds to form a40 nm hole/80 nm pitch resist pattern.

Evaluation

The DOF, the CDU, the minimum hole dimension, and the pattern shape wereevaluated by the following methods using the contact hole pattern.

DOF

The DOF (pitch/hole size) was measured using the 40 nm hole/80 nm pitchresist pattern. The dimensions of the resist pattern were measured fromabove using a scanning electron microscope (“CG4000” manufactured byHitachi High-Technologies Corporation). The DOF measurement results areshown in Table 8.

CDU

The 40 nm hole/80 nm pitch resist pattern was measured from above usinga scanning electron microscope (“CG4000” manufactured by HitachiHigh-Technologies Corporation). The hole diameter was measured at anarbitrary 24 points. The 3σ value that indicates the distribution of themeasured values was calculated, and taken as the CDU. The results areshown in Table 8.

Minimum Hole Dimension

The resist film was subjected to reduced projection exposure through apattern that was designed so that the pattern pitch after reducedprojection exposure became 80 nm (diameter), and the minimum holedimension was measured while increasing the dose to evaluate theresolution. The resolution measurement results are shown in Table 8.

Pattern Shape

The cross-sectional shape of a 40 nm hole/80 nm pitch resist pattern wasobserved using a scanning electron microscope (“S-4800” manufactured byHitachi High-Technologies Corporation). The hole diameter Lb at thebottom of the resist pattern and the hole width La at the top of theresist pattern were measured. A case where “0.9<(La/Lb)<1.1” wassatisfied was evaluated as “A”, and a case where “0.9<(La/Lb)<1.1” wasnot satisfied was evaluated as “B”. The pattern shape evaluation resultsare shown in Table 8.

When Using Another Developer

Each item was evaluated in the same manner as described above, exceptthat methyl n-pentyl ketone or anisole was used as the developer insteadof butyl acetate. The evaluation results obtained when using methyln-pentyl ketone as the developer are shown in Table 9, and theevaluation results obtained when using anisole as the developer areshown in Table 10.

TABLE 8 Lithographic evaluation (developer: butyl acetate) Resistunderlayer Contact hole evaluation film-forming Radiation-sensitiveresin PEB temperature Sensitivity DOF CDU Minimum hole dimensioncomposition composition (° C.) (mJ/cm²) (μm) (nm) (nm) Pattern shapeExample 40 P-10 J-3 105 32.5 0.1 1.4 38 A Example 41 P-10 J-5 85 27.50.1 1.2 36 A Example 42 P-10 J-7 100 26.0 0.1 1.5 40 A Example 43 P-10J-9 105 27.5 0.1 1.5 40 A Example 44 P-10 J-13 85 29.0 0.1 1.4 38 AExample 45 P-10 J-14 105 30.0 0.1 1.1 36 A Example 46 P-1 J-3 105 33.00.1 1.5 40 A Example 47 P-16 J-3 105 32.5 0.1 1.4 39 A

TABLE 9 Lithographic evaluation (methyl n-pentyl ketone) Contact holeevaluation Resist underlayer Radiation-sensitive PEB temperatureSensitivity DOF CDU Minimum hole dimension Pattern film-formingcomposition resin composition (° C.) (mJ/cm²) (μm) (nm) (nm) shapeExample 40 P-10 J-3 105 52.0 0.1 1.3 34 A Example 41 P-10 J-5 85 43.00.1 1.1 32 A Example 42 P-10 J-7 100 41.0 0.1 1.4 36 A Example 43 P-10J-9 105 43.0 0.1 1.4 36 A Example 44 P-10 J-13 85 47.0 0.1 1.3 34 AExample 45 P-10 J-14 105 45.0 0.1 1.0 32 A Example 46 P-1 J-3 105 52.50.1 1.4 36 A Example 47 P-16 J-3 105 52.0 0.1 1.3 35 A

TABLE 10 Lithographic evaluation (developer: anisole) Contact holeevaluation Resist underlayer Radiation-sensitive PEB temperatureSensitivity DOF CDU Minimum hole dimension Pattern film-formingcomposition resin composition (° C.) (mJ/cm²) (μm) (nm) (nm) shapeExample 40 P-10 J-3 105 43.0 0.1 1.3 36 A Example 41 P-10 J-5 85 34.50.1 1.1 34 A Example 42 P-10 J-7 100 33.0 0.1 1.4 38 A Example 43 P-10J-9 105 35.0 0.1 1.4 38 A Example 44 P-10 J-13 85 37.0 0.1 1.3 36 AExample 45 P-10 J-14 105 37.0 0.1 1.0 34 A Example 46 P-1 J-3 105 43.50.1 1.4 38 A Example 47 P-16 J-3 105 43.0 0.1 1.3 37 A

As is clear from the results shown in Tables 8 to 10, the resistpattern-forming method according to one embodiment of the inventioncould form a contact hole pattern that exhibited an excellent DOF, CDU,resolution, and pattern shape when using an ester, ketone, or etherorganic solvent as the developer when performing a plurality of exposuresteps.

The resist pattern-forming method according to the embodiments of theinvention can thus deal with various resist patterns (e.g., trenchpattern and hole pattern), and can form a resist pattern that exhibitsan excellent depth of focus, an excellent pattern shape, highresolution, excellent CDU, excellent pattern collapse resistance, andthe like. Therefore, the resist pattern-forming method may suitably beused for lithography for which a reduction in line width will beincreasingly desired in the future.

Obviously, numerous modifications and variations of the invention arepossible in light of the above teachings. It is therefore to beunderstood that within the scope of the appended claims, the inventionmay be practiced otherwise than as specifically described herein.

1-8. (canceled)
 9. A resist pattern-forming method comprising: applyinga resist underlayer film-forming composition to a substrate to form aresist underlayer film, the resist underlayer film-forming compositioncomprising (A) a polysiloxane; applying a radiation-sensitive resincomposition to the resist underlayer film to form a resist film, theradiation-sensitive resin composition comprising: (a1) a polymer thatchanges in polarity and decreases in solubility in an organic solventdue to an acid; and (a2) a fluorine-containing polymer, exposing theresist film; and developing the exposed resist film using a developerthat comprises at least one organic solvent selected from the groupconsisting of an alcohol, an ether, a ketone, an amide, an ester and ahydrocarbon.
 10. The resist pattern forming method according to claim 9,wherein the polysiloxane (A) is a hydrolysis-condensation product of atleast one silane compound comprising a silane compound shown by aformula (i),R^(A) _(a)SiX_(4-a)  (i) wherein R^(A) represents a hydrogen atom, afluorine atom, an alkyl group having 1 to 5 carbon atoms, an alkenylgroup, an aryl group, or a cyano group; the alkyl group represented byR^(A) is unsubstituted, or at least one hydrogen atom of the alkyl grouprepresented by R^(A) is substituted with a glycidyloxy group, anoxetanyl group, an acid anhydride group, or a cyano group; the arylgroup represented by R^(A) is unsubstituted, or at least one hydrogenatom of the aryl group represented by R^(A) is substituted with ahydroxyl group; X represents a halogen atom or —OR^(B), wherein R^(B)represents a monovalent organic group; a is an integer from 0 to 3; in acase where a plurality of R^(A) are present, each of the plurality ofR^(A) is either identical or different; and in a case where plurality ofX are present, each of the plurality of X is either identical ordifferent.
 11. The resist pattern-forming method according to claim 9,wherein the resist underlayer film-forming composition further comprises(B) a nitrogen-containing compound.
 12. The resist pattern-formingmethod according to claim 9, wherein the resist underlayer film-formingcomposition further comprises (C) a photoacid generator.
 13. The resistpattern-forming method according to claim 9, wherein the polymer (a1)comprises a structural unit (I) shown by formula (1),

wherein R represents a hydrogen atom or a methyl group; and each ofR^(p1), R^(p2), and R^(p3) individually represents a monovalenthydrocarbon group having 1 to 20 carbon atoms; or R^(p1) represents amonovalent hydrocarbon group having 1 to 20 carbon atoms, and R^(p2) andR^(p3) bond to each other to form a divalent alicyclic hydrocarbon grouphaving 4 to 20 carbon atoms together with a carbon atom bonded to R^(p2)and R^(p3).
 14. The resist pattern-forming method according to claim 9,wherein the polymer (a2) does not comprise an acid-labile group.
 15. Theresist pattern-forming method according to claim 9, the resistpattern-forming method being used to form a trench pattern, a holepattern or both thereof.
 16. The resist pattern-forming method accordingto claim 9, wherein a content of the at least one organic solvent in thedeveloper is 60 mass % or more based on a total amount of the developer.17. The resist pattern-forming method according to claim 9, wherein acontent of the at least one organic solvent in the developer is 80 mass% or more based on a total amount of the developer.
 18. The resistpattern-forming method according to claim 9, wherein a content of the atleast one organic solvent in the developer is 90 mass % or more based ona total amount of the developer.
 19. The resist pattern-forming methodaccording to claim 9, wherein the resist underlayer film-formingcomposition further comprises (B) a nitrogen-containing compound, and(C) a photoacid generator.